Volume 1 Submission

Group Synergy:
In general the group worked effectively as a team. Most members attended the group meetings.
However, the group was faced with an unforeseen challenge. Indeed, James Finlayson was not present
for the majority of the project for personal reasons. In addition, he insisted on taking on work with
the promise to deliver. Nevertheless, after a few weeks no work was sent back to the group and
communication was difficult and mainly one-sided. This sequence of events was repeated several
times as James reappeared periodically (every few months) for 1-3 days. A lot of group effort went
into redistributing his work to other group members which led to major delays.
This information was added as per Dr. Ahns request as it largely influenced the group dynamics over
the course of the project. We were unaware of the severity of James conditions. However, we are
sympathetic and wish him a speedy recovery.
Production of High Purity Hydrogen with CO 2

Capture
Volume 1
Group 1:
Jennifer Coyle - s1227207
Jack Mercer - s1240259
Elissa Mui s1219617
Qi-Shaun Wong s1302249
Aidan Cairnie - s1102723
Yongjun (John) Chen - s1105812
Astrid Stroobants - s1202301
James Finlayson
Table of Contents
1
INTRODUCTION AND DESIGN ........................................................................................................................ 2
PROCESS SELECTION ..................................................................................................................................... 6

2.1
DESULPHURISATION OF THE FEED ............................................................................................................................. 6
2.1.1
Initial Considerations................................................................................................................................. 6
2.1.2
Options for Desulphurisation of the Feed ................................................................................................. 6
2.2
WET BASED PROCESSES........................................................................................................................................... 6
2.3
DRY BASED PROCESSES ........................................................................................................................................... 7
2.4
CONCLUSION ........................................................................................................................................................ 8
2.5
HYDROGEN PRODUCTION........................................................................................................................................ 8
2.5.1
Steam Methane Reforming (SMR) ............................................................................................................ 8
2.5.2
Partial Oxidation (Pox) .............................................................................................................................. 8
2.5.3
Autothermal Reforming (ATR)................................................................................................................... 9
2.5.4
Conclusion ................................................................................................................................................. 9
2.6
CARBON CAPTURE (CC) ........................................................................................................................................ 10
2.6.1
Pressure/Vacuum Swing Adsorption ....................................................................................................... 10
2.6.2
Chemical Absorption ............................................................................................................................... 10
2.6.3
Membrane Reactors ................................................................................................................................ 11
2.6.4
Sorption Enhanced Reaction Process ...................................................................................................... 11
2.6.5
Chemical Looping .................................................................................................................................... 12
2.6.6
Cryogenic Capture ................................................................................................................................... 12
2.6.7
Conclusion ............................................................................................................................................... 13
2.7
HYDROGEN PURIFICATION ..................................................................................................................................... 14
2.8
CONCLUSION ...................................................................................................................................................... 14
PROCESS FLOW DIAGRAM AND PROCESS DESCRIPTION ............................................................................... 15

3.1
PROCESS FLOW DIAGRAM FOR DESIGN 1 ................................................................................................................. 15
3.2
DESIGN 1 ........................................................................................................................................................... 16
3.2.1
Process Description ................................................................................................................................. 16
3.2.2
Process Control ........................................................................................................................................ 17
3.2.3
Heat Integration Design 1 ....................................................................................................................... 18
PROCESS FLOW DIAGRAM FOR DESIGN 2 .................................................................................................... 20

4.1
DESIGN 2 ........................................................................................................................................................... 21
4.1.1
Process Description ................................................................................................................................. 21
4.1.2
Process Control ........................................................................................................................................ 21
4.1.3
Heat Integration Design 2 ....................................................................................................................... 22
ENERGY AND MATERIAL BALANCES ............................................................................................................. 23

5.1
ASSUMPTIONS MADE ........................................................................................................................................... 23
5.2
DESIGN 1 ........................................................................................................................................................... 23
5.2.1
Overall Mass Balance .............................................................................................................................. 23
5.2.2
Overall Energy Balance ........................................................................................................................... 23
5.3
DESIGN 2 ........................................................................................................................................................... 24
2
5.3.1
5.3.2
Overall Mass Balance .............................................................................................................................. 24

Overall Energy Balance ........................................................................................................................... 25
THERMODYNAMICS AND CHEMISTRY ......................................................................................................... 26

6.1
DESIGN 1 ........................................................................................................................................................... 26
6.1.1
Reactions ................................................................................................................................................. 26
6.1.2
Separations ............................................................................................................................................. 28
6.2
DESIGN 2 ........................................................................................................................................................... 32
6.2.1
Reactions ................................................................................................................................................. 32
6.2.2
Separations ............................................................................................................................................. 33
HAZARDS AND SAFETY ................................................................................................................................ 34

7.1
CHEMICAL HAZARDS ............................................................................................................................................ 34
7.2
PROCESS HAZARDS .............................................................................................................................................. 36
7.2.1
General Plant Hazard .............................................................................................................................. 36
7.2.2
Desulphurisation Unit.............................................................................................................................. 36
7.2.3
Furnace .................................................................................................................................................... 36
7.2.4
Pre-Reformer, Steam Methane Reformer (SMR) .................................................................................... 36
7.2.5
Water Gas Shifters .................................................................................................................................. 36
7.2.6
PSA Unit................................................................................................................................................... 36
7.2.7
MEA Carbon Capture Unit ....................................................................................................................... 37
7.2.8
Chemical Looping Combustion Reactors ................................................................................................. 37
7.3
HAZARDS RANKING .............................................................................................................................................. 37
ENVIRONMENTAL IMPACT .......................................................................................................................... 39

8.1
GENERAL ............................................................................................................................................................ 42
8.2
FLUE GAS TREATMENT AND DISPOSAL ...................................................................................................................... 42
8.3
SOLID WASTE DISPOSAL ........................................................................................................................................ 43
8.4
LIQUID WASTE DISPOSAL ....................................................................................................................................... 43
ECONOMIC ANALYSIS OF THE TWO DESIGNS ............................................................................................... 44

9.1
INTRODUCTION AND ASSUMPTIONS ........................................................................................................................ 44
9.2
ESTIMATING THE TOTAL CAPITAL COST.................................................................................................................... 44
9.3
ESTIMATING THE TOTAL VARIABLE COSTS ................................................................................................................ 45
9.4
ESTIMATING THE HYDROGEN AND CO2 REVENUES, AND NATURAL GAS ANNUALISED COST .............................................. 45
9.4.1
Hydrogen Revenues................................................................................................................................. 46
9.4.2
CO2 Revenues .......................................................................................................................................... 46
9.4.3
Natural Gas Costs .................................................................................................................................... 46
9.5
ESTIMATING THE TOTAL COST OF PRODUCTION ........................................................................................................ 47
9.6
ESTIMATING THE ANNUAL NET PROFIT .................................................................................................................... 47
9.7
CALCULATING THE ANNUAL DEPRECIATION OF THE PLANT .......................................................................................... 47
9.8
DISCOUNTED CUMULATIVE CASH FLOW, NPV AND UNCERTAINITY OF THE TWO DESIGNS ............................................... 47
10
START UP AND SHUT DOWN ................................................................................................................... 49
11
RECOMMENDATIONS AND CONCLUSIONS ............................................................................................... 54
List of Figures
Figure 1-1: Hydrogen Market Distribution [2] .................................................................................................................. 3
Figure 2-1: Process flow diagram for chemical absorption[42] ...................................................................................... 10
Figure 2-2: Process flow diagram of CLC[48] .................................................................................................................. 12
Figure 2-3: Process flow diagram of cryogenic CC[53] ................................................................................................... 13
Figure 3-1: Process Flow Diagram for Design 1 .............................................................................................................. 15
Figure 4-1: Process Flow diagram for design 2 ............................................................................................................... 20
Figure 6-1: PSA Adsorption Isotherm [63] ...................................................................................................................... 29
Figure 6-2: PSA Adsorption Isotherm [63] ...................................................................................................................... 29
Figure 6-3: CO2 loading as a function of its partial pressure [65] .................................................................................. 31
Figure 11-1: Proposed designs ........................................................................................................................................ 54
List of Tables
Table 1-1: Product specifications ...................................................................................................................................... 2
Table 2-1: SWOT of the two proposed Desulphurisation Techniques .............................................................................. 8
Table 2-2: SWOT for Hydrogen production techniques .................................................................................................... 9
Table 2-3: SWOT analysis for Carbon Capture techniques ............................................................................................. 13
Table 2-4: Proposed Designs ........................................................................................................................................... 14
Table 3-1: Design 1 HEN ................................................................................................................................................. 19
Table 4-1: Design 2 HEN .................................................................................................................................................. 22
Table 5-1: Overall Mass Balance for Design 1 ................................................................................................................. 23
Table 5-2: Overall Energy Balance for Design 1, Part 1................................................................................................... 23
Table 5-3: Overall Energy Balance for Design 1, Part 2................................................................................................... 24
Table 5-4: Overall Mass Balance for Design 2 ................................................................................................................. 24
Table 5-5: Overall Energy Balance for Design 2 .............................................................................................................. 25
Table 6-1: Reactions in Design 1 ..................................................................................................................................... 26
Table 6-2: Rates of Reaction in Design 1 ......................................................................................................................... 27
Table 6-3: Pre-exponential factors and Equilibrium Constants in Design 1.................................................................... 27
Table 6-4: Adsorption Constants in Design 1 .................................................................................................................. 28
Table 6-5: PSA cycles ....................................................................................................................................................... 29
Table 6-6: Reactions in Design 2 ..................................................................................................................................... 32
4
GROUP 1
The University of Edinburgh School Of Engineering

Volume 1
Chemical Engineering Design: Projects 4
Table 6-7: Kinetic data for CLC ........................................................................................................................................ 32
Table 7-1: Hazardous information process chemicals .................................................................................................... 34
Table 7-2: Hazard ranking ............................................................................................................................................... 37
Table 7-3: Hazard and Risk Safety Sheet......................................................................................................................... 38
Table 8-1: Design 1 Material inventory list ..................................................................................................................... 39
Table 8-2: Design 2 Material inventory list ..................................................................................................................... 41
Table 9-1: Calculated steps involved in the estimate of the Total Capital Investment .................................................. 45
Table 9-2: Calculated annual operating cost for each design ......................................................................................... 45
Table 9-3: Expected prices for the products and feedstock ........................................................................................... 46
Table 9-4: Revenues and Feed Costs .............................................................................................................................. 47
Table 9-5: Total Cost of Production of both Designs ...................................................................................................... 47
Table 9-6: Annual Net Profit of both designs .................................................................................................................. 47
Table 9-7: Expected price of H2 ....................................................................................................................................... 48
Table 11-1: Summary table for both designs .................................................................................................................. 54
GROUP 1

Volume 1
Introduction and Design
Design Brief
The design brief stated that a high purity hydrogen production plant with integrated Carbon Dioxide Capture must
be designed. The plant was required to have a capacity of 5 tonnes/h of product hydrogen and was to be situated
near a chemical production site in the United Kingdom. All utilities were readily available including our natural gas
feed supply, which was available by pipeline at 33 bar(a). The final requirement was the pressurisation of the carbon
dioxide product to 150 bar(a) for transportation. Carbon dioxide and hydrogen had specific product composition
requirements, detailed below.
Table 1-1: Product specifications
Component
Carbon dioxide, CO2
Carbon monoxide, CO
Methane, CH4
Oxygen, O2
Nitrogen, N2
Hydrogen, H2
Moisture
Total Carbons
Carbon Dioxide Product

Minimum 97%
Maximum 3%
2%
0.01%
3%
3%
-
Hydrogen Product
< 5vpm
< 100vpm
>99.98%
< 8vpm
< 10vpm
Discussion of Design Remit in a Chemical Engineering Context

Process Background: Hydrogen can be produced using various processes, which can be defined according to four
different categories. The first of which, thermochemical processes, which release hydrogen from organic material
such as fossil fuels and biomass using heat and reforming reactions. Next, electrolytic processes use electricity to
split water into hydrogen and oxygen. Then, solar processes also operate through the splitting of water. Finally, the
fourth type of hydrogen production centers on Biological processes, where micro-organisms such as bacteria and
algae produce hydrogen.[1] Biological and solar processes are currently still at an early stage of research, while
electrolytic and thermochemical processes contain well-developed technologies. However, as electrolytic processes
incur large capital costs and energy inefficiencies, thermochemical processes are prevalent in industrial applications.
The design options for hydrogen production via thermochemical processes were limited with the awareness of our
natural gas feed. Three options were identified; Steam Methane Reforming (SMR), Partial Oxidation and Autothermal Reforming. SMR technology is by far the most advanced with many industrial scale operations and is also
the best performing in terms of energy efficiency for hydrogen production. First introduced in 1930, SMR is
preferential compared with other methods due to its high yield of hydrogen. Several hydrogen production facilities
operate with SMR technology, for example Linde has a plant located in Texas producing approximately 10 t/hr of
H2.[2]
With respect to Carbon Capture technologies, this aspect of the plant has a vibrant process background with
multiple innovative processes emerging in recent years. Various carbon capture techniques can be implemented in
fossil fuel based plants with three categories identified; post-combustion capture, pre-combustion capture and oxyfuel combustion. Post-combustion captures carbon dioxide from the flue gas, while pre-combustion captures the
carbon dioxide after a syngas stream passes through a Water Gas Shift reactor. Oxy-combustion capture uses oxygen
to replace air in combustion, creating a stream of concentrated CO2 and water. For comparison and innovation,
Design 1 utilises a post-combustion capture technology whilst Design 2 integrates an oxy-combustion capture
approach. The most common technique currently used in industry is the Chemical Absorption technique with
Monoethanolamine (MEA). As Carbon Capture is a relatively new technology, level of maturity was a considerable
aspect when selecting a method.
Historical Developments: The hydrogen production part of the plant is well established as opposed to the carbon
capture section which relies on techniques that are still being developed and improved. In recent years various
processes have progressed from the laboratory to a pilot plant: Pressure Swing Adsorption of flue gas in Port Arthur
by Air Products[3], Membrane separation in the flue gas in Wilsonville by the National Energy Technology
Laboratory[4] and finally Chemical Looping Combustion in Germany at the Technical University of Darmstadt.[5]
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Amine absorption is also being used in industry at the Boundary Dam project by Saskpower[6]. These groundbreaking projects are key to the development and improvement of Carbon Capture techniques.
Alternative Technologies: For both hydrogen production and carbon capture there are numerous technologies
available. Coal gasification is a popular production method of hydrogen when coal is used as a feedstock. Partial
Oxidation and Autothermal Reforming are alternatives to SMR with respect to hydrogen production. For carbon
capture, there are many alternatives to Chemical Looping Combustion (Design 2) and MEA Absorption (Design 1).
Technologies for capturing carbon dioxide include Cryogenic capture, Membranes, Pressure Swing Adsorption and
Sorption Enhanced Reaction. Please refer to Process Selection in Section 2 for a full analysis of the different
processes feasible for natural gas feed.
Market Studies: The market research undertaken provides important information to identify and analyse the market
need, market trends and commodities pricing. It encompasses both qualitative and quantitative information to
assess the current situation surrounding hydrogen production and CCS both in the U.K. and worldwide. Furthermore
a hypothetical plant location is discussed.
Commodities Pricing
Carbon Dioxide: The EU emissions trading system (EU ETS) is currently in practice to combat climate change and
effectively reduce greenhouse gas emissions. It is the biggest international trading scheme for greenhouse gas
emission allowances and covers power stations, airlines and many more areas of pollution. With a Carbon Capture
facility integrated into the process carbon taxing would be avoided and income generated through selling CO 2
emission allowances. Currently the allowance price is EUR 4.85 /tonne CO2 [7] while the market price for CO2 ranges
between 3.50-13/ tonne depending on logistic costs.[8]
Natural Gas: Natural gas currently sells for 28.5 p/therm, which converts to 160/t, as of March 2016. Natural gas
prices have not been this low for twenty years, [9] but due to the market trend discussed on page 4, it is expected
for the price to remain at or close to this figure. As a result, 160/t was used for the economic analysis in Section 9.
Figure 1-1: Hydrogen Market
Hydrogen: Hydrogen market prices show great variation depending on the
Distribution [2]
form of delivery, consumed volume, location and contract length; in the
past, prices have ranged from 715 to 3170/tonne [10] in todays money.
The most common (mode) value for hydrogen was found to be $3/kg, which
converts to 2250/t H2 in todays money. An expected value of 2360/tonne
was calculated using Swansons Rule (Refer to Appendix C). Please refer to
Section 9: Economics for more information.
Supply and Demand
Carbon dioxide is heavily valued in many industries, and has a number of
purposes; precursor to chemicals, foods, beverages & wine making, inert
gas for pressurised systems, agricultural and biological applications,
enhanced oil recovery and as a refrigerant.
As the plant is producing significant amounts of carbon dioxide, it is realistic
to suggest the carbon dioxide will be sold locally, within the UK via truck.
The main area of focus for selling would be the food and drink industry as
there are several potential companies to sell to located all over the UK.
Due to the food and drink industry requiring a specific quality of carbon
dioxide in their products by law, our product may need to be pre-treated
first. Ultimately this would affect the market selling price. If unsuitable for
the food and drinks industry applications carbon dioxide can also be piped off-shore for enhanced oil recovery in the
oil and gas sector.
Natural gas production has spiked in the past two years due to the dramatic increase of U.S. shale gas extraction.
Supply therefore is abundant, with Argentina and China both drilling numerous shale gas wells for a stake in the
market. However with growth in China the weakest since the global financial crisis, worldwide demand for natural
gas is declining. These global effects will increase the global supply and hence the availability of natural gas in the
UK.
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Hydrogen can be utilised in the production of soap in the chemical industry, and can therefore be sold to nearby
soap manufacturing businesses such as 'Soapworks' located outside Glasgow. Since the purity of the hydrogen
product is specified to be 99.98 %, there is potential to sell to ammonia plants within the UK, such as Billingham
plant in Teeside. The demand of hydrogen in the global market can be seen in Figure 1-1.
Market Trends
It is expected that natural gas will continue to increase its share of the global energy mix, growing at 2% per year
until 2020[11] due to its clean combustion advantage. This increase in supply suggests a future reduction in natural
gas purchase price. Consequently, the feedstock expense for the plant would decrease.
World consumption of hydrogen is expected to increase annually by 3.5% through to 2018 to 300 billion cubic
metres.[12] The primary reason being the increase of hydrogen usage in refinery hydro-processing in developing
countries in Asia. Any surge in demand will increase profitability of the plant, with plant product expansion possible
within flexibility limits.
Carbon dioxide is a key component in Enhanced Oil Recovery. As the Oil and Gas industry seeks to increase oil
output whilst reducing operating costs, EOR techniques are becoming ever popular with a substantial demand for
CO2.
Location
The plant must be situated in an area away from local population but close enough for a reliable of supply of
feedstock to reach. The National Grid can provide electricity, while transportation links and storage must also be
considered. The central belt in Scotland is one candidate for a location for the hydrogen production facility. It is also
close to Glasgow where Soapworks could be a potential buyer of the hydrogen product. Similarly, the heavily
industrialised area of Teeside in North-East England will also have utility connections available and Billingham
ammonia plant is nearby to buy hydrogen.
Necessary Constraints and Implications on Design Options
There were a number of constraints imposed on the design; which were limiting factors on design options. The main
constraints surrounded the final products, as discussed in Design Brief, on page 1.
The high purity of hydrogen requirement influenced the choice of purification process. Pressure Swing Adsorption
(PSA) is selected due to its ability to produce a hydrogen purity of 99.9%. PSA however has the drawback of reduced
recovery rates, with 10.4% of hydrogen in Design 1 sent back to the Furnace post-PSA for combustion. This loss of
hydrogen will impact the overall efficiency of the plant, and hence affect profitability.
The natural gas feed was specified to contain 5.1 ppm(wt) sulphur. A desulphurisation unit was therefore necessary
to remove the sulphur, preventing catalyst poisoning downstream. Two design options were explored in depth for
desulphurisation; Iron Oxide/Sulfatreat and Amine Absorption. After comparing preliminary calculations, the
Sulfatreat method was selected due to its superior performance. Please refer to Process Selection, Section 2, for a
full review of each method.
Carbon dioxide is required to be compressed to 150 bar(a) for transportation needs.
Global Assumptions and Implications on Design Options
For simplification and short cut design it was necessary to include some comprehensive assumptions. In terms of
feed, we assumed that supply is reliable and stored in a hold up tank on-site. Furthermore, no product storage
facilities are included as it is assumed that products are instantly transported to buyers.
With a focus on combustion, both designs assume complete combustion of fuel when providing a heat generation
for the endothermic SMR reaction. As a result, the total production of carbon dioxide may be overly optimistic and
provide a degree of inaccuracy in the economics. Concerning plant emissions NOx formation, and hence discharge, is
assumed to be zero. This assumption is valid regarding thermal NOx formation as the furnace does not operate
above 1700K the temperature where significant formation occurs[13]. The assumption also holds for fuel NOx, as
neither combustive fuel in design 1 or 2 contains pre-ionized nitrogen.[14] Lastly, NOx formation can occur through
molecular nitrogen in the air combining with fuel during combustion. This creation is called Prompt NOx and the
amount formed is often debated, but presumed negligible at high temperatures. [14] However, low NOx burners are
implemented in Design 1 and accounted for in the process economics. For Chemical Looping Combustion in design 2,
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one of the advantages surrounds the fact that no NOx form due to the fuel and air streams never directly mixing.
Therefore the assumption for short cut design is credible.
In both designs, perfect separation was assumed for each water knock-out drum. In reality this assumption is
invalid, however it was deemed acceptable for short cut purposes. The presence of carbonic acids may induce
corrosive issues, and so the materials of construction would need to be thoroughly assessed.
The cyclone, C-201, flue gas (stream 21) in Design 2 is assumed to be dispersed to atmosphere (after heat recovery)
without incurring dangerous toxicity levels of nitrogen for personnel.
Regarding the sulphur feed specification, it is assumed that H2S is the only sulphur based component present in the
feed, and therefore the only sulphur based component that requires removal. This focused the research of
desulphurisation methods towards H2S removal, in preference to COS (carbonyl sulphide), organic sulphur
compounds and mercaptans removal.
Design Objectives and Priorities
Profitability: The primary economic objective is to design a profitable hydrogen production plant with integrated
carbon capture. The economics of Design 1 and 2 are compared to provide an indication of where maximum
profitability can be achieved. Heat integration is paramount in order to find the minimum energy requirement in
each design, and hence minimise the energy costs. Please refer to Economics, Section 9, for a further information
and analysis.
Safety: The main priority is to ensure the plant is safe for personnel to operate within, and for the general public to
live around. Careful consideration is given to control schemes and hazardous materials, such as MEA and Nickel
Oxide. Please refer to Safety and Hazards, Section 7, for further details. Equipment is designed with safety factors in
mind in terms of material of construction, operating conditions and size.
Emissions: Emission limits were sought for the hazardous materials and discharges in the plant. The objective to
never exceed these limits - this is achieved except for an uncertainty regarding our MEA emissions. However, an
improvement to the process is suggested to reduce MEA emission limits to trace levels. Section 8 details our
environmental impact and the Critical Review, Section 10, goes into process modifications in more detail.
Literature Survey (and extended limitations)
The sources used to construct these designs were taken from a wide variety of literature for enhanced credibility.
Reference was made to scientific journals, reputable news and industry websites, conference papers, textbooks, and
Edinburgh University lecture material. The majority of scientific papers sought for design methods and verification
were highly peer reviewed, aiding to the reliability of the report.
Due to the nature of this preliminary design and short cut procedures, the designs carry certain limitations which are
discussed further in Critical Review, Section 10. However, two designs are presented with justifications and fulfill all
pre-requisites and design objectives.
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Volume 1
Process Selection
The plant was divided into four main sections: desulphurisation, hydrogen production, carbon capture and hydrogen
purification. For each of these different sections different techniques were considered and compared to each other
in order to choose the best options for the design phase. The evaluation of each of these techniques consisted of an
environmental, safety, economical and maturity analysis which was complimented by a SWOT (strength weaknesses,
opportunities and threats) analysis and a scoring system (Appendix F).
2.1 Desulphurisation of the Feed
2.1.1 Initial Considerations
It was decided that a desulphurising unit was required in both designs due to the presence of sulphur in the natural
gas feed (5.1 ppm wt).[15], [16], and [17] suggest that hydrogen sulphide (H2S) is usually the most prevalent sulphur
compound present followed by mercaptans and organic sulphur compounds. As the sulphur compound in the feed
was never explicitly specified, it was assumed that only hydrogen sulphide (H2S) was present. In addition, it was
found from [18] that H2S concentrations in the order of 5 ppm poisons the (nickel) catalyst used in the SMR process.
While the provided natural gas feed is only slightly above the suggested poisoning concentration, it was decided that
a desulphurising unit would be used to remove the H2S completely or down until extremely trace amounts.
Desulphurisation would therefore be the first process in both designs as its goal is to ensure that there is no H2S in all
of the downstream processes. In addition, this section of the plant would also treat the fuel gas used in H 2
production.
2.1.2 Options for Desulphurisation of the Feed
Desulphurisation processes are usually split into two distinct categories which are wet or dry based processes. Only a
select few desulphurisation processes were considered for use in the plant.
2.2 Wet based processes
Description: The operating principle is that the H2S in the feed gas stream will be absorbed using basic solution of
most commonly monoethanolamine (MEA), Diethanolamine (DEA), or hot potassium carbonate. In addition, MEA
process derivatives like the Sulfiban process are modern variations of the basic MEA system where a few other
chemicals are added to minimise degradation of the amine sorbent. Almost all absorption based desulphurisation
processes are scalable with great flexibility toward the concentration of H2S in the feed.
Maturity: The basic MEA process was developed in the 1920s; the Sulfiban process has been commercially used
since 1954. As of 1978, around 100 units had been constructed, treating a combined gas volume of 4.7 x 10 7 m3 per
day[19]. In essence, MEA based processes are considered the standard way to treat sour gas in the chemical
industry.
Technical: The sour feed gas enters the bottom of an absorber while the lean amine solution (often 12-30 wt% MEA)
enters the top. The purified product gas leaves the top of the absorber and should be clean enough to continue to
the SMR reactor. The sulphur-rich amine solution is pumped to the stripping column where it is heated and reverse
chemical reaction occurs, stripping the acid gases into the vapour phase, where they are treated for sulphur
recovery. The sulphur-lean amine solution is returned to the absorber.
The reactions occurring in the absorber are as follows:
2 + ( )
Eq. 1
( ) + 2
Eq. 2
Reactions in the stripper are the exact reverse of these. A process flow diagram (figure G-2) can be found in
Appendix G.
Environmental: In general, amine based desulphurisation processes release very little to the surroundings due to
regeneration of the sorbent. However, MEA, DEA, Caustic Soda or other absorbents are usually highly soluble in
water and present a serious threat to aquatic environments. Safe disposal will incur additional taxes due to the
active nature of the absorbents.
Economic: Regenerative absorbent based processes for desulphurisation like MEA are considered economical for
treating high H2S concentrations (2% mole fraction+) in the feed. The ability to scale the process with H2S
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concentration gives it an edge when it comes to treating variable or very sour feed gas streams. However, absorption
based processes are not known for use in ultra-purification and may not be the best choice for this plant.
Safety: Amines do cause mild chemical burns if exposed to the skin or ingested. At temperatures above 250 C MEA
can spontaneously combust in self-sufficient exothermic reaction. Pressures are low in the absorber and around 2
bar (g) in the stripper. Temperatures range from around 32 C in the feed to 115 C in the stripper. With proper
control, it appears that the MEA absorption option is inherently the safest option of the wet processes.
2.3 Dry based processes
Description: Dry based desulphurisation processes are almost always adsorption based and very similar in terms of
operation. They only differ in the type adsorbent used. Examples of adsorbents used in dry based desulphurisation
methods are iron, zinc or metal oxides, activated carbon and molecular sieves (zeolites). Additionally, modern
variants like Sulfatreat (iron oxide) improve on the physical properties of the adsorbent as well as reduce the
operating requirements and considerations. References such as[15], [17], [19] and[16] provide a satisfactory range
of dry based desulphurization methods but only the iron oxide variant Sulfatreat and zinc oxide method will be
discussed here.
Maturity: Sulfatreat takes it roots from the iron oxide desulphurisation process which is a very mature process and
has been in use since the 1850s. It was generally one of the more favoured methods for desulphurising low H2S
concentrations in feed streams but had an inherent safety problem due to its exothermic nature when reacting with
air[20] which would ignite the support material (wood). Sulfatreat solves this problem by using non-pyrophoric
support material. Similarly, zinc oxide guard beds have been in use throughout the 1900s and is the preferred
method for ultra-purification.
Economic: Sulfatreat and Zinc oxide based desulphurisation methods are cheap when compared to MEA or
absorptive based processes. However, this is only true for low H2S concentrations in the feed. Above a certain
threshold (1200 ppm for iron oxide and much lower for zinc oxide[19]), this method of desulphurisation becomes
uneconomical due to the large volume of adsorbents required. Additionally, this also means that large variations in
the feed H2S concentrations will cause problems for these processes.
Technical: Dry based desulphurisation processes all operate on the same principle which is to feed sour gas through
a fixed (or fluidised) bed of adsorbent material in a lead/lag design. This means that it is essentially a batch process
which continues to sweeten the feed gas until the sulphur loading point is reached and the bed has to either be
regenerated or dumped. An example of the iron oxide process with the relevant chemical equations from [20] is
provided below.
1
1
() + () () + ()
3
3
Eq. 3
= 22 25 1
The PFD (figure G-3) in Appendix G represents a typical flow sheet for the iron oxide desulphurisation process but
can be applied to almost all other dry based desulphurisation processes. In this two-column design, one column will
undergo gas sweetening via adsorption and the other will either be on standby, regenerating or dumped and
replaced with fresh adsorbent. In some cases, water is added to saturate the feed stream, which enhances the
adsorptive capabilities of the adsorbent (iron oxide). However, zinc oxide based processes must operate dry
otherwise the adsorbent material will be ruined.
Environmental: In terms of environmental impact, most dry based desulphurisation processes are material heavy
and require change-outs every year or quarter year depending on the estimated breakthrough time. However, the
spent adsorbents are usually inert in nature and require no special disposal considerations. For example, spent
Sulfatreat is essentially pyrite which is both safe, inert and reusable as supplement material in bricks, roads and sand
stabilisers[21]. Zinc oxide on the other hand is not as environmentally friendly and is indeed toxic to aquatic bodies
but present no problems otherwise[22].
Safety: Almost all dry based adsorbents are safe to handle and present no safety risk to the staff or the plant. Iron
oxide was an example of a fire hazard earlier but the modern variant of it completely solves the problem. Table F-2
shows the SWOT of the Desulphurisation Section; the resulting scoring matrix is in Appendix F, Table F-1.
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Volume 1
Conclusion
Table 2-1: SWOT of the two proposed Desulphurisation Techniques
Strengths
Amine absorption or
similar wet based
processes (Sulfiban
process)
Flexibility in
sulphur removal
Weaknesses
May incur large
operating and capital
expenses that far
outweigh low sulphur
removal applications
Opportunities
Possibility to save
on material costs
due to
regeneration
Low release to
environment
Threats
Additional costs
due to tail gas
treatment unit to
separate H2S and
CO2 waste gas
stream
Dry based
limited H2S
Good removal
Not able to cope
desulphurisation
concentration operating
Economical for
efficiency for low
with high H2S feed
processes (Sulfatreat,
range with significant
current plant
H2S applications
streams
Zinc oxide)
waste material footprint
Dry based desulphurisation via Sulfatreat (Iron oxide) is our primary choice for desulphurisation as it is able to
reliably remove the trace H2S concentration in the feed from 5.1 ppm (wt%) down to < 0.1 ppm (wt%) whilst still
being very economical when compared to the wet based amine absorption desulphurisation method. The scoring
matrix for the proposed desulphurisation techniques are presented in Appendix F, Table F-2.
2.5 Hydrogen Production
There are three main processes used for producing H2 from natural gas.
2.5.1 Steam Methane Reforming (SMR)
Description: Steam methane reforming is a traditional method used to convert natural gas to syngas, it requires an
external heat source due to the endothermic reactions that occur. This method for producing reformate can
therefore only achieve its potential when effective heat integration in the plant can be conducted. Subsequently, in
what is called the "water-gas shift reaction," the carbon monoxide are converted to carbon dioxide and increasing
the concentration of hydrogen at the same time. Finally, a process step called "pressure-swing adsorption (PSA) is
used, which will be covered in a later section. [23-26]
Maturity: SMR has been around for more than 80 years. It was first introduced in 1930 and has been the leading
method for producing hydrogen at large scale. Examples of SMR plant would be the one located in Texas from Linde
with a capacity of 10 tonnes/hr and Air product have major hydrogen pipelines in places such as Lousiana USA and
Rotterdam in the Nether. [2, 24, 27]
Technical: In steam-methane reforming, methane reacts with steam (700 C -1000 C) under high pressure in the
presence of a nickel catalyst to produce hydrogen, carbon monoxide, and a relatively small amount of carbon
dioxide. The main processes involved are[28]:
: + + 3
Eq. 4
: + +
Eq. 5
Safety: Safety hazard of dealing with flammable gases like methane and hydrogen under a high temperature is
considerable, however with the maturity of this production method, appropriate control techniques and procedures
exist.
Economic: The cost of conventional steam reforming catalysts is relatively low although they tend to be vulnerable
to the sulphur-based catalyst poisons. According to a survey conducted by Petroleum energy centre in 1999 [29]
SMR has the highest relative cost out of the three technologies, it was used as a based case and has been given 100
as the value.[30]
2.5.2 Partial Oxidation (Pox)
Description: In partial oxidation, hydrocarbons in natural gas react with a rich air-fuel ratio. The reaction products
contain primarily hydrogen and carbon monoxide (and nitrogen, if the reaction is carried out with air rather than
pure oxygen), and a relatively small amount of carbon dioxide and other compounds. Subsequently, in a water-gas
shift reaction, the carbon monoxide are converted to carbon dioxide and increasing the concentration of hydrogen
at the same time.[25, 26]
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Maturity: Partial oxidation is a relatively new process compared to SMR. It has been around for about 30 years, an
example plant in industrial scale would be the located one in Texas by Eastman Group. [31]
Technical: Methane reacts with air (1000 C - 1400 C) under 125 bar pressure in the presence of a microlith-based
catalyst to produce hydrogen and carbon monoxide. It is an exothermic process and is typically much faster than
steam reforming and requires a smaller reactor vessel. As seen in the reaction equations below, the process initially
produces less hydrogen per unit of the input fuel than that of steam reforming.[28] [32]
The main processes involved equation 5 and 6 [28, 32]:
1
Eq. 6
+ + 2
2
Safety: The control of the oxygen/air flowrate must be strictly accurate, otherwise the reaction instead of being
partial oxidation, will become complete combustion, the volume of the end products are much larger than the
original expected ones, the gas expansion could lead to an explosion of the reactor in the worst case scenario.
Economic: According to a survey conducted by Petroleum energy centre in 1999 [29] Pox is slightly cheaper in terms
of relative cost compared to SMR, it was given a value of 95 compared to 100 given to SMR. This can be interpreted
as 5% cheaper than the SMR method. However it was stated in the Petroleum energy centre in 1999 [29] that the
economy evaluated for Pox is just an estimation. [30]
2.5.3 Autothermal Reforming (ATR)
Description: ATR combines the exothermic nature of partial oxidation and the endothermic steam reforming
reaction to balance the heat requirements, giving an advantage of a thermally neutral system, while providing
reasonable hydrogen yield. The reactor tends to be relatively moderate in cost and size. Reactions occur over steam
reforming catalysts located in close proximity to the partial oxidation catalysts. The quality of the ATR reformate,
defined in terms of hydrogen mole fraction, is thus superior to the CPOX reformate but not as good as the SMR
reformate. [26, 33]
Maturity: ATR is a relatively new technology and is still under continuous development. There are only a few
example plants; one of them would be the plant located in South Africa by SASOL. [33]
Technical: In Autothermal Reforming, methane reacts with steam (1000-1400 C) under 125 bar pressure in the
presence of either nickel or microlith-based catalyst to produce hydrogen and carbon monoxide.[28]
The main process involved is [28]:
Eq. 7
+ (1 ) + + (3 ) 0 < < 1
2
Safety: On the downside, a more extensive control system is needed for ATRs to ensure a safe and robust operation
of the fuel processing system.
Economic: According to a survey conducted by Petroleum energy centre in 1999 [29] ATR was given a value of
ranging from 85 - 95 compared to 100 given to SMR. This can be interpreted as 5 - 15% cheaper than the SMR
method. [30]
2.5.4
Conclusion
Table 2-2: SWOT for Hydrogen production techniques
Strengths
Weaknesses
SMR
High level of maturity

High purity of hydrogen
Require external heat

from the furnace
CPOx
An exothermic process
Relatively new process
Thermally neutral system
Very precise control

system to integrate
the process heat
ATR
Opportunities
Threats
Most conventional
method: reliable
Many recent
developments on newer
technologies
Mainly used for smaller

scale (less than 1
tonne/h of H2)
More suitable for very
large scale (greater than
20 tonne/h of H2)
Very limited information
Very limited information

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SMR is our primary choice for hydrogen production as it achieves the highest yield of H2 and it is the most mature
and leading technology in producing large scale of hydrogen. The scoring matrix for the proposed hydrogen
production techniques are in Appendix F, Table F-3.[34]
2.6 Carbon Capture (CC)
In a Hydrogen Production Plant, there are various streams that contain CO2. The figure G-1 in Appendix F indicates a
simplified block flow diagram of the Hydrogen Production Plant in which the streams containing a significant amount
of CO2 are identified. It can be seen that CC systems can be located in three different places. From a first look CC at
position 3 seems the best option as CO2 from the hydrogen production line and from combustion could be captured
while CC at position 1 and 2 do not enable the capture of CO2 formed during the combustion process. However, the
pressure in stream 3 is lower therefore the volume and equipment will be bigger. There are various CC techniques at
various stages of maturity. The main techniques that were considered in this project are as follows: (1) Pressure or
Vacuum Swing Adsorption (P/VSA), (2) Chemical Absorption, (3) Membrane Reactors, (4) Sorption Enhanced
Reaction Process (SERP), (5) Chemical Looping (CL) and (6) Cryogenic Capture.
2.6.1 Pressure/Vacuum Swing Adsorption
Description: This technology is based on the physical binding of gas molecules onto an adsorbent. The process
operates at relatively constant temperatures and relies on alternating pressure to perform adsorption and
desorption. It is estimated that high purity CO2 (97%) could be obtained using PSA at position 3 and that the CO2
emissions can be reduced by 90%[35].
Maturity: P/VSA has been used for many years for hydrogen purification. However, the application of P/VSA for CC is
still being tested. Indeed, in Port Arthur a VSA project by Air Products is in operation since 2013[3] to test the
application of VSA for CC in position 3 of figure 7. The project consists of a large scale DEMO that eventually will
capture one million tons of CO2 annually. This CO2 would then be purified to 97%[3]. The project cost $431million[3].
In 2015, VPSA post-combustion carbon capture reached a Technology readiness level of 5[36].
Technical: this CC technique would come at an efficiency penalty of 15% for an IGCC[37]. Zeolites are the most
common adsorbents. In order to provide a continuous supply of CO2, a minimum of four adsorption vessels are
required[38].
Environmental/Safety: Zeolites are safe adsorbents. They do not have flammable or explosive properties[39]. In
addition to that they are not considered to be toxic, carcinogenic or irritating to the skin and no accumulation in
organism is to be expected[39]. If the adsorbent is ingested or inhaled repeatedly or in high doses the substance may
cause kidney damage[39].
Economic: In recent studies, the capital cost of the PSA CC was estimated to be 800 103US$/MW[36] and the fixed
O&M was estimated to be 23.41 103 US$/MW[40].
2.6.2 Chemical Absorption
Description: CO2 is separated from the
flue gas by passing the flue gas
through a continuous scrubbing
system. This system is composed of an
absorber and a desorber. The
absorption process is based on the
reversible chemical reaction of CO2
with an aqueous alkaline solvent,
usually an amine. In the desorber, CO2
is stripped from the alkaline solution
and the regenerated solvent is sent
back to the absorber.[41]
Maturity:
Chemical
absorption
systems have been in use since the
1930s for the capture of CO2 from
Figure 2-1: Process flow diagram for chemical absorption[42]
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ammonia plants and hence, are a commercially realized technology in various sectors (power plants, food
industry,...)[41]. This technology has been used in the first CC project for power plants: Boundary Dam project by
SaskPower[6].
Technical: MEA can reduce CO2 emissions by 75% at an efficiency penalty of 11%[37].
Safety: MEA can cause burns to the eyes and skin. It is also harmful if inhaled, swallowed or absorbed through the
skin. It can cause lung damage if aspirated, and repeated exposure may cause liver and kidney damage. MEA is highly
corrosive. [43] Contact with iron or steel MEA can form an unstable crystalline complex: tris(ethanolamino)-iron. This
compound can ignite when heated to 5471C in the presence of air[43]. Due to its water solubility and reactivity
with other compounds, MEA biodegrades rapidly and is not likely to bioaccumulate in the aquatic food chain. Studies
on a wide variety of freshwater fish show that MEA has very low toxicity to fish. [43] MEA exhibits good temperature
stability. Nevertheless, at temperatures above 250C, it can undergo a self-sustaining exothermic reaction, causing
rapid decomposition. [43]
Economic: Studies have been conducted using Aspen to predict how post-combustion carbon capture would affect
the operation of a natural gas powered power plant. A natural gas flowrate of 167.3 Ib/hr was used as a basis and a
90% carbon capture requirement was set. The efficiency drops from 50.2% to 42.2%. The total as spent capital cost
increases from 771$/kW to 1637$/kW. The cost of electricity also increases from 58.9$/kWh to 87.2$/kWh. The first
year CO2 avoided cost is 87.3$/tonne. [44, 45]. MEA has also been tested in industry and recent studies estimated
that the capital cost of MEA was 613 103US$/MW while the fixed O&M was estimated to be 24.52 103US$/MW[37].
2.6.3 Membrane Reactors
Description: Membrane reactors combine reaction with separation to increase conversion. One of the products of a
given reaction is removed from the reactor through the membrane, which shifts the equilibrium of the reaction to
the products (according to Le Chatelier's Principle).
Maturity: More research needs to be conducted to enable the production of a membrane that combines a thin layer,
high flux, and stability in all operating conditions. Membrane materials other than Palladium could provide an
inexpensive alternative and could be explored.
Environmental/Safety: Palladium has no adverse effects on humans. In terms of the environment, palladium metal
has relatively low toxicity. It is however harmful to some plants in salt form.
Economic: Higher CO conversions are attainable with lower temperatures, meaning potential gains can be made
with prolonged catalyst life, enabling lower production and material costs. Furthermore, the simultaneous CO2
capture and generation of extra pure H2, eliminates traditional WGS reactors and PSA. However, the expensive
nature of Palladium could be of concern. The incremental total capital requirement (TCR) for capture was estimated
to be 334US$/kW and the incremental Cost of Electricity (COE) was estimated to be 9.0US$/MWh[46].
2.6.4 Sorption Enhanced Reaction Process
Description: This technique involves combining CC with the Steam Methane Reforming (SMR) process. During the
reforming CO2 is adsorbed onto a sorbent which is generally calcium oxide following the following reaction.
+
Eq. 8
The CO2 can then be desorbed in-situ using pressure swing adsorption leading to solvent regeneration and pure CO2
capture. By removing one of the products of the reforming process, the equilibrium is shifted to the product side,
which leads to an increased production of hydrogen. Also, reformation takes place at a significantly lower
temperature (300-500C) than conventional SMR process (800-1000C) while achieving the same conversion of
methane to hydrogen. There is a minimization of side reactions such as coking. Therefore, hydrogen is produced at
relatively high purity directly from the reactor.
Maturity: The concept of a combined reaction and separation in hydrogen production is not new. Indeed, RostrupNielsen reports that the first description of addition of a CO2-acceptor to a hydrocarbon steam reforming reactor
was published in 1868 (by Tessiedu Motay and Marechal). More recently, the SEPR and the use of calcium-based CO2
sorbents has been demonstrated and intensively studied by a group at Louisiana State University (USA).
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Environmental/Safety: Calcium Oxide is not combustible but contact with water or moisture may generate sufficient
heat to ignite combustible materials. It is also not considered to be an explosion risk. However, it is toxic and when
inhaled it can severely irritate the upper respiratory tract and ulceration and perforation of the nasal septum may
occur from extended exposure. As a corrosive substance, when ingested it may attack the oesophagus resulting
in abdominal pain, nausea and vomiting and it may cause serious alkali burns in the mouth and throat. It is also a
skin irritant and it may damage eye tissues causing redness, tearing, blurred vision and pain. In addition to that, it is
toxic to aquatic life.
Economic: Initially it seems the cost would be reduced, as there is no need for WGS reactors. However, a study
estimated that by including a sorption enhanced water gas shift in a hydrogen production and power plant in order
to capture 96% of the CO2 led to an additional cost of 75.9/t CO2. [47] The incremental total capital requirement
(TCR) for capture was estimated to be 365US$/kW and the incremental Cost of Electricity (COE) was estimated to be
11.2 US$/MWh[46].
2.6.5 Chemical Looping
Description: Chemical looping can be included in a hydrogen production
plant in two different ways: Chemical Looping Combustion and Chemical
Looping Steam Reforming. The Chemical Looping Combustion process is
similar to conventional steam reforming but the furnace is replaced with a
CLC system. This is an indirect combustion system that avoids the direct
contact of fuel with the oxidant. The system is split into two reactors: a
reduction reactor (fuel reactor) and an oxidation reactor (air reactor). The
oxygen is brought to the fuel via a solid carrier constituted of a metal oxide
material. In the fuel reactor the fuel reduces the solid oxide material. It is
then transported to the air reactor where the reduced metal oxide is
oxidized again with air. Also, CL can be included in the steam methane
reforming process. It can produce highly concentrated H2 and CO2 as the
reaction products. The CL-SMR system consists of fuel reactor (FR) for CH4
oxidation and steam reactor (SR) for steam reduction, where oxygen
carriers (metal oxides) circulate between the two reactors. Chemical
Looping reactors are fluidised beds.
Figure 2-2: Process flow diagram of

CLC[48]
Maturity: Chemical looping combustion (CLC) dates from the early 1980s when it was proposed as a system for
augmenting power station efficiency[49]. A number of CL concepts are being researched around the globe to test the
system design and to estimate capital and operating costs for commercial-scale systems. Currently, NETL supports
several CL projects in collaboration with industry, academia, and NETLs Office of Research and Development (ORD)
ranging from lab and bench scale testing to evaluation of pilot-scale prototypes. [50, 51] Nowadays, Chemical
looping for oxy-combustion has reached a TRL of 6 as it has been demonstrated at 1MWth pilot plant using hard coal
and ilmenite as oxygen carrier where the total time of operational experience exceeds 7000h[36]. Presently, more
than a thousand materials have been tested in the laboratory. Also, from testing, it was established that >99%
conversion of the fuel can be obtained and that 100% CO2 capture is possible using gaseous fuels[36]. Chemical
looping reforming however has been tested in a pilot plant.
Environmental/Safety: There should be no formation of thermal NOx since the regeneration of the carrier is
achieved at moderate temperatures. The exit streams are relatively clean. The exit stream of the fuel reactor is
mainly composed of water and CO2 while the exit stream from the air reactor is mainly composed of nitrogen and
oxygen. Most metal oxides are toxic to aquatic life. Dust is irritating to the eyes, skin and respiratory system. Eye
contact may cause corneal damage. In addition it may cause dermatitis.
Economic: A study estimated that by including CLC in a hydrogen production and power plant in order to capture
93.5% of the CO2 led to an additional cost of 81.5/t CO2. [47] The incremental total capital requirement (TCR) for
capture was estimated to be 413US$/kW and the incremental Cost of Electricity (COE) was estimated to be 13.1
US$/MWh[46].
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2.6.6 Cryogenic Capture

Description: CCC (Cryogenic Carbon Capture) uses phase change to separate CO2 and other pollutants from exhaust
or process gases. In CCC the CO2 is cooled to such a low temperature (about -140 C) that it desublimates - changes
from a gas to a solid. The solid CO2 is separated from the remaining gas, pressurized, melted, and delivered at
pipeline pressure. Cryogenic Carbon Capture (CCC) is a post-combustion technology that has the potential to reduce
carbon emissions from fossil-fuelled power plants by 9599%, at half the cost and energy of current state-of-the-art
carbon capture processes. In addition, CCC also removes other pollutants, such as SOX, NOX, and mercury. [52]
Maturity: Cryogenic separation is widely used commercially for high CO2 concentration streams - typically above
90% - but it is not used for more dilute streams.
Environmental/Safety: The heat integration aspect provides a certain amount of safety as no external heat sources
are required. This also improves the environmental aspect as no energy is wasted for heating purposes.
Economic: Cryogenic carbon capture is estimated to cost less than $30 per ton of captured CO2, this could make
cryogenic capture a favourable option. Water may have to be removed before the gas stream is cooled to avoid
blockages, incurring further costs. For dilute streams the energy associated with cooling can increase operating
costs. [52]
Figure 2-3: Process flow diagram of cryogenic CC[53]

2.6.7
Conclusion
Table 2-3: SWOT analysis for Carbon Capture techniques
Strengths
Weaknesses
Opportunities
Threats
PSA
Safe adsorbent
Low maturity
High purity CO2
High cost
MEA
Low temperatures and

pressures
Corrosive
SERP
Low temperatures
Harmful sorbent
CLC
No formation of thermal
NOx
Harmful sorbent
Membranes
High SMR conversions
Surface poisoning
Cryogenic
Energy efficient
Removal of water additional step
Small flexibility in flue

gas composition
Sorbent regeneration
No water-gas shift
Higher purity H2
Higher conversion
Carrier can be
regenerated
Less harmful exit
stream
Increased H2
production
Reduced cost
Energy intensive
Not mature enough
Durability
Durability
Not mature enough
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Even though cryogenic capture, chemical looping reforming and Sorption enhanced reaction process seem like very
promising technique they were not chosen as the maturity level is very low which would impact the reliability of the
design. Amine absorption was on the other hand chosen because it has been tested in industry. Out of the remaining
techniques PSA and CL, CLC seemed to me more promising from an economical viewpoint. Membranes were also
chosen as it can lead to higher conversions of methane.
2.7 Hydrogen Purification
Many hydrogen plants that were designed and built 20 or more years ago rely on a hot potassium carbonate or MEA
chemical absorber (as explained in section 1.3.2) to remove CO2 and a methanator to convert the remaining CO 2 and
CO to methane and water. Methanation is the catalytic hydrogenation of CO2 to methane also called the Sabatier
reaction[54]:
+ 4 + 2
= 252.9/
Eq. 9
The final product however only achieves a purity of 95-97%[55]. This purity does not satisfy the product
requirements for this plant, therefore this option was not considered in further detail. More recently hydrogen
plants rely on a PSA unit (as explained in section 1.3.1) to purify the reactor effluent. The use of PSA enables a 99.9%
product purity[55]. The off-stream of the PSA can be used as a fuel source to supply the required energy to the SMR.
2.8 Overall process selection conclusion
The two final proposed designs are summarised in table 2-4. Sulfatreat was chosen as the feed natural gas
desulphurisation technique for both designs due to it being very economical for treating low quantities of sulphur in
the feed; additionally the bed is safe to dispose and poses little risk to the environment. For design 1, the more
traditional design, it was decided to go with the more mature technologies of conventional SMR with Amine
Absorption Carbon Capture of the flue gases, whereas design 2 utilises the more modern technology of membrane
SMR with integrated Chemical Looping Combustion to capture the CO2. Finally, design 1 utilises pressure-swing
adsorption to purify the hydrogen to product specification, whilst in Design 2 a simple two-phase separator is used
to purify the hydrogen from water.
Table 2-4: Proposed Designs
Desulphurisation
Reaction
CC
H2 purification
Design 1
Sulfatreat
SMR
MEA
PSA
Design 2
Sulfatreat
Membrane SMR
CLC
Water knock-out
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3
3.1

Volume 1
Process Flow Diagram and Process Description for Design 1

Process flow diagram for Design 1
Figure 3-1: Process Flow Diagram for Design 1

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3.2

Volume 1
Design 1
3.2.1 Process Description

Desulphurisation: The natural gas feed (stream 1) enters the plant at 33 bar(a) and ambient conditions. P-101
functions as a back-up compressor in case the inlet feed is at a lower than expected pressure (maximum 9%
deviation to feed pressure). Stream 1a is then heated in E-101 to 30oC, as slightly elevated temperatures enhance
the adsorption process. To further enhance adsorption, stream 1b can be water saturated via stream U1 but this is
dependent on the adsorbent employed. Stream 2 then enters the desulphurisation section, which is comprised of
two adsorption columns, T-101 A/B, each filled with an iron oxide (Sulfatreat) bed. The desulphurisation columns
operate at 30oC and 33 bar(a). While one column is operational, the second column is emptied. This process achieves
total sulphur removal so as to avoid catalyst poisoning downstream. The adsorbed sulphur and spent bed (stream
U2) are sent to landfill.
Pre-reformer: The desulphurisation outlet (stream 3) splits into two streams: stream 4 and stream U6. U6 is sent to
the furnace through compressor P-201 for subsequent combustion. Stream 4 is sent through the furnace and is
additionally heated through E-204 to 400oC. Make-up steam (stream U3) combines with stream 4 to achieve the
required 0.3 steam to carbon ratio in stream 5. Stream 5a then enters the pre-reformer, R-201.
In the pre-reformer cracking occurs when the stream reacts with a bed of nickel catalyst on an aluminium oxide
support. This reduces all of the higher hydrocarbons down to methane. Due to side reactions, partial conversion of
methane to hydrogen occurs. All reactions are exothermic and the temperature of the outlet stream (stream 6)
reaches 415oC. The pre-reformer operates at 400oC and 32.9 bar(a).
SMR: Stream 6 mixes with a further steam input, utility stream U4 to increase the steam to carbon ratio. Stream U4
flowrate is three times as large as the flowrate of methane in stream 6 in order to reach this ratio. The combined
stream (stream 7) is heated to 950oC in the furnace, E-204. Afterwards stream 7a flows through the SMR tubes in
reactor R-202, located in the radiant section of E-204.
The SMR reactor, operating at 30 bar(a) and 950oC, is composed of multiple parallel tubes containing a nickel
alumina catalyst. This environment causes the methane to react with steam, producing hydrogen and carbon
monoxide. A side reaction occurs between the steam and the carbon monoxide to produce carbon dioxide and
hydrogen. The net heat of reaction is endothermic (Hr,298K = 206.kJ/mol). The outlet of R-202 (stream 8) is cooled in E201 to 450oC before entering the high temperature WGS, R-203.
WGS: In the high temperature WGS, R-203, carbon monoxide reacts with steam to produce the two desired products
hydrogen and carbon dioxide. This reaction is exothermic (Hr,298K =-41.2kJ/mol), with the reactor operating at 30
bar(a) and 450C. Following on from this, stream 9 is cooled to 250oC in E-202 before entering the low temperature
WGS, R-204. The same exothermic reaction occurs only at this lower temperature and over a different catalyst
(copper/zinc based). The outlet of the low temperature WGS (stream 10) is cooled in E-203 to condense and hence
remove the water. Stream 10 then enters vessel V-202 where the water (stream U5) separates. The vapour products
including H2, CO, CO2 and N2, (stream 11) is sent to the Pressure Swing Adsorption unit.
PSA: Pressure Swing Adsorption involves a number of columns, operating at various pressure stages to produce high
purity (99.9%) hydrogen. The designed PSA unit cycle schedule contains several steps; Feed (F), Equalisation 1 (EQ1),
Equalisation 2 (EQ2), Equalisation 3 (EQ3), Purge Preparation (PP), Blowdown (BD), Purge (PU) and Feed Recovery
(FR). There are also corresponding Equalisation Receiving steps, (EQR1, EQR2 and EQR3). For simplification stream
11 is assumed to be a binary mixture of CO2 (20%) and H2 (80%) in design methods.
Operation of the PSA unit starts with an explanation of the cycle schedule for a single column (T-306) from start to
end. Starting with the feed step, the binary gas mixture is passed through T-306 at 30C and 25 bar(a). Hydrogen is
the least likely to be adsorbed and so passes through to the outlet at (>99.99%) purity via stream 12 while the 20%
mixture of CO2, N2 and hydrocarbons are adsorbed onto the activated carbon/zeolite adsorbents. After the feed step
(250 seconds est.), T-306 undergoes pressure equalization with T-304, followed by T-303 and T-302 to save on repressurising the vessel upon purging. After that, T-306 undergoes purge preparation with T-301, which is a similar
step to pressure equalisation but with T-301 undergoing purge. Blowdown then proceeds which sends the now CO2,
N2 and hydrocarbons rich stream along with some of the unrecovered H2 to the furnace via stream 13. After that, T301 now undergoes purge which also sends the off-gas to the furnace followed by receiving equalisation and finally
16
GROUP 1

Volume 1
re-pressurisation by feed. The cycle then starts again from the feed step. As the cycle schedule for a single column is
now known, the other columns T-302 through T-306 will undergo similar steps in a sequence defined by the PSA
cycle schedule table which is presented in Section 6: Thermochemistry, Table 6-5.
Furnace: From the PSA unit, stream 13 is combined with air utility streams; U6 and U7. U6 provides a 1.1 air to fuel
ratio entering the furnace, E-204, undergoing combustion. The furnace provides the necessary heat for the SMR
reaction, and to pre-heat streams 4 (pre-reformer inlet) and 7 (SMR inlet) convectively. The flue gas (stream 16) is
then cooled to 40oC through E-401 and stream 16a then enters the MEA unit. The furnace operates at ambient
pressure and 950oC, producing 119MW of power.
Monoethanolamine (MEA) Absorption: Flue gas, stream 16, is cooled in E-401 to 40oC before entering water knockout drum V-401 to remove the condensed water. The vapour outlet, stream 17, is then compressed to 3.1 bar(a) to
promote the transfer of mass from the vapour phase into the liquid phase. It is assumed pressurising to 3.1 bar(a)
creates a pressure drop sufficient enough to propel the outlet gases up through the absorber to the stack. The gas is
then cooled again to the optimum temperature for absorption, 40 C, while further condensed water is removed by
knock-out drum V-402. The vapour outlet (stream 18) containing N2, CO2, water vapour and excess O2, is then fed
into the bottom of the trayed absorption unit, T-401, for absorption of CO2 using MEA into the liquid phase.
An exothermic chemical reaction occurs in T-401, which binds the MEA and CO2 together into the liquid phase with
the water. The liquid outlet (stream 19) is called the rich amine since there is a high molar loading of CO2 per mole of
MEA in the solution. The rich amine is heated by E-404 to 70 C prior to entering the stripping column, T-402.
The stripping column attains high recovery rates of CO2 into the vapour phase. The reaction is endothermic and so
heat is provided by reboiler E-403, heating the column to 120 C. The liquid outlet from the reboiler (stream 24)
contains very little CO2 and therefore is called the lean amine stream. This is combined with the MEA-water recycle
stream R6 (itself a combination of two water-MEA recycles R1a and R2) to form an aqueous solution which is slightly
under 30 wt% MEA. This is then pumped into surge drum V-403 to allow for a constant lean amine flowrate to enter
the top of the absorber T-401 as stream 25c. Thus ends the amine circulation at steady state, any MEA lost out the
top of the absorber is recovered in MEA-water recycle stream R3, and likewise before CO2 compression in recycle
stream R4. It is assumed for simplicity of the design that MEA does not degrade over time.
CO2 Compression: The vapour outlet of the reflux drum (stream 28) is cooled to ambient conditions in order to
condense out MEA and water for separation in V-501, leaving 99.98% pure CO2 with 0.02 % Nitrogen (stream 29). It
must be noted that this assumption of 100 % separation of liquid water from gaseous CO2 was a design simplification
which significantly reduces the amount and cost of separation equipment. This high-purity CO2 stream is compressed
in a series of three centrifugal compressors, P-501, P-502 and P-503. Intercoolers E-503, E-504 and E-505 reduce the
temperature of the CO2 to 25 C before each subsequent compression. After the final stage of compression and
cooling, the CO2 by-product is at 70 bar(a) and 25 C which means it is in liquid state. It is then routed to hold-up
tank V-502 before being pumped to 150 bar(a), ready for distribution and sale.
3.2.2 Process Control
Desulphurisation: Control is paramount on the desulphurisation unit to prevent sulphurous feed entering the
process downstream and damaging catalysts. Should breakthrough point be close, the composition control (CC103/105) sends a signal to send the remaining gas into the standby column (T-101B). Temperature indicators (TI104/106) are also placed on the columns across stream 2 linked to E-101 to ensure feed is at 30 C. Pressure
indicator (PI-109) ensures downstream pressure requirements are met by linking to back up compressor P-101. A
sample point has been provided to ensure sufficient sulphur removal has occurred. Pressure safety valves to flare
prevent the column from over-pressurization.
Pre-reformer: A pressure relief valve to be used in the case of an emergency is situated on the pre-reformer.
Multiple temperature indicators (represented by TI-204) along the side of the reactor at regular intervals measure
temperature changes and indicate the completion of the reaction.
SMR: A high-high temperature level alarm and trip system is attached to the SMR (not shown on PFD) to stop fuel
flowing into the furnace and generating more heat. The SMR outlet temperature is controlled through TIC-208 which
regulates the fuel inlet stream. Composition control (CIC-218) attaches to a steam make-up utility stream to ensure
the optimum ratio enters the furnace.
17
GROUP 1

Volume 1
WGS: A high-high temperature level alarm and trip system (not shown on PFD) activates a cooling jacket on both
HWGS (R-203) and LWGS (R-204).
PSA: Composition indicator CIC-310 changes the step cycle times, with composition control usually being a PI
controller or variant. Differential pressure indicators are linked to the CIC for the pressure equalization step.
Pressure indicator PI-303 in the feed must show 25 bar pressure as inlet pressure has to be kept high to ensure
higher partial pressure of adsorbate. Temperature indicators must show a bed temperature around 30C to ensure
high levels of adsorption. Flow valves are located at feed inlet for protection in case of composition control failure. A
pressure safety valve fitted to the vessels transport vapour to flare due to avoid a potential H2 rich release.
Furnace: A composition indictor controller, CIC-218, is placed on stream 14 to measure the composition of
hydrocarbons in the fuel gas line. Air utility stream U3 is then adjusted accordingly to ensure complete combustion
in the furnace. A temperature indicator, TI-301, is fixed at the end of the convection section of the furnace to
monitor the flue gas temperature. Fuel input should be reduced if the temperature is too high. Sample point, SP219, is located at the furnace outlet (stream 15). Analysis is then carried out to check for concentrations of carbon
monoxide, hydrocarbons and carbon. Presence of these components indicates incomplete combustion and that
more air is needed.
Monoethanolamine (MEA) Absorption: For the stripping column, T-402, temperature indicator TIC-404 is placed on
the outlet reboiler stream to ensure the column will not exceed 125C. The temperature for the reboiler is set to be
120C so that there is a safety margin for operation fluctuations. Temperature control reduces MEA thermal
degradation and the generation of other undesired corrosive products.
For the absorption column, T-401, composition control (CI-408) of the CO2 flowing to the stack is controlled by
manipulation of the lean amine inlet (stream 25c). The flowrate of flue gas from the furnace (stream 18) must be
measured since it will likely fluctuate. The flowrate of the lean amine (stream 25c) will therefore be manipulated to
allow for both the changing flowrate of the furnace gas and also the composition of CO2 emitted above the absorber.
Temperature of absorber gas inlet (stream 18) is maintained at 40 C by manipulating the flowrate of coolant to E402. The level of lean amine solution in surge drum V-403 must be maintained at a safe level by manipulation of the
flowrate of stream 25a into the drum. High and low level trips are installed (not shown on PFD) on surge drum V-403
to help prevent the surge drum from filling or running dry.
CO2 Compression: Level control is achieved in liquid CO2 hold-up tank V-502 by manipulating the inlet flowrate of
stream 29f. Temperature control is incorporated on all heat exchanger outlets by manipulating the flowrate of
coolant to the relevant heat exchanger.
3.2.3 Heat Integration Design 1
Figure A-3 in Appendix A summarizes the suggested heat exchanger network with data support from Table 3-1 for
design 1. Following this, it was evident that there was no pinch temperature in design 1 due to the very large
amounts of cooling required with not enough complementing process streams to use the heat. HINT calculated the
pinch temperature to be 1290 [K] (no pinch) with 189 [MW] of cooling utility required using a minimum temperature
difference of 10 [K]. The actual cooling required will be greater (~250 [MW]) since not all hot streams were taken
into account even though all cold streams were tabulated. The most likely cause for this no pinch case is due to an
overdesigned furnace. Currently, the furnace pre-heats two important energy intensive streams which are the prereformer and SMR pre-heating streams. Each of these streams require ~30 MW of energy each in order to preheat.
Therefore, by reducing the size of the furnace and allocating these streams to the HEN, the amount of heating utility
may be reduced and a pinch can be obtained.
However, the current unaltered design more than manages to meet the heating energy required which means that
no additional hot utility will need to be purchased other than for start-up purposes. To ease reading, Table 3-1 is
provided below to walk the reader through streams in the HEN. Finally, it is important to note that E-6XX series heat
exchangers (required for full heat integration) were not shown on the PFD so as to keep it concise but will mean that
additional heat exchangers will be designed specifically for process heating. Where possible, PFD heat exchangers
were included and directly referenced.
18
GROUP 1
Stream
9-9a
8-8a
16-16a
17a-17b
29e-29f
1a-1b
E-403 Utility
U4
U3

Table 3-1: Design 1 HEN
Volume 1
Stream description
Description
Cooling of the gas stream after high Used to heat utility stream U4 (liquid) then
temperature water gas shift reactor
cooled via E-202
Cooling of the gas stream after main SMR Used to heat utility stream U4 during its
reactor
phase change then cooled via E-201
Used to superheat U4 to 688 [K] then fully
Cooling of the post furnace flue gas stream
superheat U3 from liquid to 673 [K] and
and condensing the water present
finally cooled using E-401
Used to heat E-403 utility until it becomes a
Cooling and condensing the water present
saturated vapour at 406.5 [K] before being
following compression via P-401
cooled by E-402
Used to supply heat to the natural gas feed
Cooling of the compressed CO2 product
so that it can enter the desulphurization
stream before condensing at its critical
section at 303 [K] before being cooled by Etemperature
505
Natural gas feed that enters the
Heated completely using 29e-29f
desulphurization section at 303 [K]
Reboiler water that is pre-heated to
saturated steam before entering E-403 Heated completely using 17a-17b
(reboiler)
Heated completely using streams 9-9a, 8-8a
Make up steam that is required for SMR
and 16-16a before being sent to the furnace
reaction
for further heating
Make up steam that is required for the pre- Heated completely using stream 16-16a
reformer
before being sent to the pre-reformer
19
GROUP 1
4
4.1

Volume 1
Process Flow Diagram and Process Description for Design 2

Process flow diagram for Design 2
Figure 4-1: Process Flow diagram for design 2
20
GROUP 1
4.2

Volume 1
Design 2
4.2.1 Process Description

Desulphurisation: The desulphurisation section for Design 2 is exactly similar to Design 1. The desulphurisation
product (stream 3) is split into U5 and 4, to be a source of fuel for CLC and pre-reforming respectively.
Pre-reformer: Stream 4 is heated to 400 C by E-201 and is injected with steam to achieve the require 0.3 steam to
carbon ratio in the pre-reformer. The flow enters the pre-reformer, operating at 415 C and 30bar(a), to begins the
cracking process. The reactions and conditions within pre-reforming for this design are the same as those which
occur in design 1.
Membrane SMR: The pre-reformer outlet (stream 6) is expanded to 25 bar(a), before being heated to 500oC in E201. Make up steam (U4) provides a steam to carbon ratio of 2.5:1 before, the stream is sent to the SMR membrane
reactor where it is split between the multiple tubes mounted horizontally in the reactor.
Inside of each tube is a smaller tube. The space between the two tubes is filled with a nickel alumina catalyst while
steam (U10) flows through the inner tube. The inner tube is comprised of a palladium membrane, which allows the
hydrogen to pass from the SMR to the steam but keeps other gasses in the catalyst layer. Water and hydrogen flow
out from the reactor at 2bar(a) and 497oC (stream 8) and are cooled to 25oC in E-205 before entering water knockout vessel, V-301. Hydrogen is then recovered at the required product purity.
The SMR Membrane outer tube exits the reactor at 25 bar(a) and 497oC (stream 11) and is cooled through E-206 to
25C before passing through a water knock-out vessel (V-202) to separate the water. The vapour stream (stream 12)
then combines with the desulphurisation split (stream U6) before being pre-heated to 500C in E-203 for the fuel
reactor of the chemical looping system, R-202.
Chemical Looping Combustion: Compressor, P-202 provides air to the Air Reactor, R-203, which is filled with Nickel
particles supported on alumina and operates at 500C and 25bar(a). Through fluidisation the nickel particles are fully
oxidised and passed to three cyclones (stream 20) working in parallel, C-201 A/B/C. The remaining nitrogen gas is
separated from the particles and dispersed to atmosphere.
Stream 14a enters the fuel reactor, R-202, and combusts with Nickel Oxide particles from the cyclones (stream 22).
The fuel reactor operates at 500C and 25bar(a), and provides 800 kJ/mol of energy through the combustion
reaction. This energy is transferred to the SMR Membrane reaction which is highly endothermic. After reduction,
the nickel particles are transported back to the air reactor (stream 19) by gravity to re-start the cyclic process. The
fuel reactor outlet (stream 15) is comprised of carbon dioxide and water, and is cooled through E-204 before being
sent to water knock-out drum V-201 for water separation.
CO2 Compression: The carbon dioxide vapour (stream 16) exits the knock-out drum and is sent to compressor P-301
to begin pressurisation to 70 bar(a). Cooler E-301 cools the gaseous CO2 stream to the liquid, and it is subsequently
pressurised to 150 bar(a) using pump P-304.
4.2.2 Process Control
Desulphurisation: The control in Design 2 for the desulphurisation unit is the same as for Design 1. Please refer to
Section 3.2.2 for further details.
Pre-reformer: The control in Design 2 for the pre-reformer is the same as for Design 1. Please refer to Section 3.2.2
for further details.
Membrane SMR: Due to the severe consequence of high temperatures regarding the Palladium membranes, a
temperature trip system (not shown on PFD) is installed to cut inlet flow to both the CLC system and the SMR
membrane tubes. This prevents any further reaction and heat generation.
Chemical Looping Combustion: Flow indicators, FIC 210/212, are located onto the inlet streams of both reactors to
adjust the flowrate of either/both feeds to ensure sufficient combustion and heat release. A Pressure Relief Valve is
implemented onto the Air Reactor (R-203) to relieve the pressure and dispel harmless oxygen and nitrogen into the
atmosphere in the case of an emergency. To avoid the particles also leaving with the hot air in this case, a fine mesh
has been inserted into the pressure valve. A temperature indicator on the Fuel Reactor (R-202) provides a monitor in
the control room in the case of the reactor overheating. The SMR Membranes can only withstand a temperature of
21
GROUP 1

Volume 1
500C, and so it is imperative for a trip system so in the case of any temperature spike, the system is shut down to
prevent irreversible membrane damage. A temperature indicator on the Air Reactor also monitors performance over
time. A Gas Analyser, CI-216, on the outlet Fuel Reactor stream, allows full operation of CLC system once sufficient
combustion has been achieved.
CO2 Compression: The control in Design 2 for the CO2 Compression is the same as for Design 1. Please refer to
Section 3.2.2 for further details.
4.2.3 Heat Integration Design 2
Figure A-6 in Appendix A summarizes the suggested heat exchanger network with data support from Table 4-1 for
design 2. HINT calculated a pinch temperature of 507 [K] with a required heating duty of 8.36 [MW] and cooling duty
of 145 [MW] using a minimum temperature difference of 10 [K]. This takes into account almost all hot and cold
streams in the process besides stream 4-4a which was overlooked during the HEN design. In the interest of time, the
HEN was not redesigned as this problem was noticed after the HEN was completed. Further analysis will be provided
in the critical review section but a summary of the results will be presented here.
For the most part, design 2 has arguably better heat management. A key result is the heating of stream U10 which
supplies steam to the SMR-membrane reactor and stream U4 which is the SMR-membrane steam make up. Taking
this streams out of the HEN will result in a similar situation to design 1 where the pinch was at the highest available
temperature. However, doing so will result in a 22 [MW] requirement to heat stream U10 and 24 [MW] to heat
stream U4 whereas the HEN only requires 8.36 [MW] total heat utility, indicating an 80% reduction in heating utility
required. Should stream 4-4a be added during a redesign, a similar conclusion will be found. Overall however, the
cooling duty required by the HEN is still substantial and this will be further discussed in the critical review subsection.
Similar to design 1, Table 4-1 is provided below to walk the reader through streams in the HEN for design 2.
Table 4-1: Design 2 HEN
Stream
11-11a
8-8a
Stream description
Cooling of product gas exiting the SMR-membrane via
outer membrane (not in the membrane tube)
Cooling of product gas exiting the SMR-membrane via
inner membrane (membrane tube)
21-21a
Cooling of cyclone flue gas before release
15-15a
Cooling of the CO2 rich chemical looping flue gas and

condensing the water before removal
Cooling of hyper-compressed make up air for the chemical

looping air reactor
Cooling and condensing of compressed CO2 product gas
16a-16b
before pumping
Heating of natural gas feed to 303 [K] before entering the
1a-1b
desulphuriser
U9
U3
U4
U10
14-14a
6a-6b
Heating of the utility steam make up for the pre-reformer

Heating of the utility steam make up for the SMRmembrane
Heating of the utility steam make up for the SMRmembrane (not combined with feed gas)
Heating of the feed gas to be used as fuel in the chemical
looping fuel reactor
Heating of the post expanded pre-reformer product gas to
ensure that it reaches the SMR-membrane reactor at 688K
Description
Used to heat U4 (sensible) and U4 (sensible
and latent) before being cooled via E-206
Used to heat U10 (sensible), U4 (latent) and
U10 (sensible) before being cooled via E-205
Used to heat U10 (sensible), U3 (sensible)
before being cooled by E-208
Used to heat 14-14a (sensible), 6-6a
(sensible), U3 (sensible and latent), cooled
via E-204 (sensible) before final heating of
U4 (sensible)
Used to heat U4 (latent)
Used to completely heat 1a-1b (sensible)
before being cooled by E-301
Completely heated by 16a-16b
Completely heated by 21-21a, E-606 (latent)
and 15-15a
Completely heated by 15-15a, 11-11a, U9,
E-612 (latent), 8-8a, and E-609 (sensible)
Completely heated by 8-8a, 21-21a
Completely heated by 15-15a
Completely heated by 6a-6b
22
GROUP 1

Volume 1
Energy and Material Balances
5.1
Assumptions made
20% of the heat produced by the furnace is lost to the surroundings
Less than 5% of the heat produced by the CLC system is lost to surroundings
5.2
Design 1
5.2.1
Overall Mass Balance

Table 5-1: Overall Mass Balance for Design 1
Streams In
1
U1
U3
U4
U7
kg/h
2.02 x104
[-]
5.37 x103
4.02 x104
1.55 x105
Total
2.21 x105
Streams Out
12
27
30
U2
U5
U8
U9
Total
kg/h
5.23 x103
127x105
5.15x104
1.00 x10-1
1.89 x104
1.75 x104
5.52 x103
2.26 x105
Difference (kg/h)
4.82 x103
Overall percentage difference
2.19%
The table above shows the inlet and outlet streams of the plant. The values were obtained following the calculation
method described in Section 3.1 and 3.2 in Appendix D. The basis of calculation followed the standard procedure for
mass balances, with an analysis on the mass flowrates in and out of the process. The error in the overall mass
balance was found to be 2.19%. This error was considered acceptable and likely due to just rounding errors.
5.2.2 Overall Energy Balance
The overall energy balance was separated into two sections; Part one being the Desulphurisation unit to the Furnace
outlet, and part two being the MEA process to the CO2 compression train. The reason for this being the two
different methods of energy balance calculations used. The conventional energy balance equation was used for
calculations in part one, while Unisim was implemented using the amine package for energy calculations in the MEA
process. Please refer to section 3.1 and 3.2 in Appendix D for further clarification on equations utilised.
Part 1: Desulphurisation to Furnace Outlet
The energy balance is illustrated by Table 5-2. It shows the energies of the streams, energy provided by heaters and
coolers, and finally the energy of the various reactions.
Table 5-2: Overall Energy Balance for Design 1, Part 1
Energy In
1
U1
U3
U4
U7
Total
Energy In
E-101
E-205
Total
Stream Energy Balance

MW
Energy Out
-1.66 x10-1
12
0.00
16
1.16
U2
9.04
U5
-6.52 x10-1
9.37
Total
Heaters and Coolers Energy Balance
MW
Energy Out
2.23 x10-1
E-201
0.00
E-202
E-203
2.12 x101
Total
Heat Generated by Reactions
Reaction Location
Furnace
SMR
Pre reformer
HWGS
MW
1.04 x10-1
3.30 x101
1.44 x10-7
4.90 x10-2
-6.88 x101
MW
-3.34 x101
-1.15 x101
-1.13 x101
-5.60 x101
MW
1.19 x102
4.43 x101
-2.67 x10-1
-3.74
23
GROUP 1

Volume 1
LWGS
-1.97
Other Sources
Heat loss to surrounding
-2.38 x101 MW
Overall Balance
Overall difference
2.29 x101 MW
Overall percentage error
14.5 %
The error in all process sections were considered to be acceptable, except for the energy balance surrounding the
furnace. This is due to the inconsistency in the method used for calculating the enthalpy of the stream. Please refer
to section 3.1 and 3.2 in Appendix D for further explanation.
Part 2: MEA Process and CO2 Compression Train
Table 5-3: Overall Energy Balance for Design 1, Part 2
Energy In
16
MW
6.28 x102
Total
6.28 x102
Energy in
E-403
E-502
P-401
P-502
P-503
P-504
MW
5.26 x103
0.00
9.78 x101
-3.29 x103
2.60 x101
1.56 x101
Total
2.10 x103

Energy Out
27
30
U8
U9
Total
Equipment Energy Balance
Energy out
E-401
E-402
E-405
E-501
E-503
E-504
E-505
Total
Heat generated by Reactions
Absorption column
Stripping column
MW
1.41 x102
-1.70 x103
-8.07 x101
-3.64 x101
-1.68 x103
MW
-5.08 x102
-1.46 x102
-2.00 x102
-3.45 x103
-2.72 x101
-2.96 x101
-5.78 x101
-4.41 x103
-9.20 MW
-10.5 MW
Overall Balance
Overall difference
21.7 MW
0.8 %
As can be seen from the table above an error of 0.8% was obtained which was considered to be insignificant. This
result was calculated following the method in section 3.1 and 3.2 in Appendix D.
5.3
5.3.1
Design 2
Table 5-4: Overall Mass Balance for Design 2
Streams In
1
U1
U3
U4
U7
U9
kg/h
1.59 x104
0.00
5.37 x103
3.01 x104
4.00 x104
1.07 x105
Total
1.99 x105
Streams Out
U2
9
10
13
17
18
21
Total
kg/h
8.00 x10-2
5.24 x103
1.07 x105
1.05 x104
3.73 x104
5.78 x103
3.77 x104
1.97 x105
Difference
-1.92 x103
Overall percentage difference
-0.97%
The table above shows the inlet and outlet streams of the plant. The values in the table were obtained following the
calculation method described in section 3.1 and 3.2 in Appendix D. The basis of calculation followed the standard
procedure for mass balances, with an analysis on the mass flowrates in and out of the process. The error in the
overall mass balance was found to be -0.97%. This error was considered acceptable and was likely to be caused by
rounding errors.
24
GROUP 1
5.3.2

Volume 1
Overall Energy Balance

Table 5-5: Overall Energy Balance for Design 2
Energy In
1
U1
U3
U4
U7
U9
MW
-1.20 x10-1
0.00
1.04
8.47
-1.69 x10-1
3.01 x101
Total
3.93 x101
Energy in
E-101
E-201
E-202
E-203
P-101
P-202
P-304
P-301
Total
MW
1.60 x10-1
4.01
1.86
6.32
0.00
7.03
4.90 x10-1
1.31
2.12 x101

Energy Out
U2
9
10
13
17
18
21
Total
Energy out
E-204
E-205
E-206
E-207
E-301
P-201
P-203
MW
-1.03 x101
-1.06 x102
-1.33 x101
-1.05
-1.31
-2.40 x10-2
-2.72 x10-1
-1.32 x102
Total
Heat Generated by Reactions
Reaction
CLC
Membrane SMR
Pre Reformer
MW
1.04x10-7
0.00
-6.55 x101
-5.38
4.9x10-1
-2.97
4.52
-6.88 x101
MW
-3.24 x101
-3.33 x101
-2.41 x10-1
Other Sources
Heat loss to surrounding
1.29 MW
Overall Balance
Overall difference
1.23 MW
2.03 %
As can be seen from the table above an error of 0.25% was obtained which was considered to be insignificant. This
result was calculated following the method in section 3.1 and 3.2 in Appendix D.
Excel online was used for overall flowsheets in Design 1 and 2. This allowed all group members to keep up-to-date
with flowsheet and design changes.
25
GROUP 1

Volume 1
Thermodynamics and Chemistry
This section will focus on the thermodynamics behind the design of reactors and separators. This section is divided
into two parts: Design 1 and Design 2. These are divided further to discuss reactions and separations.
6.1
Design 1
6.1.1 Reactions
All reactions taking place is reactors in Design 1 are summarised in the table below:
Table 6-1: Reactions in Design 1
1
2
+ 6 13 + 6
+ 5 11 + 5
Hrx (298K)
(J/mol)
79600
59210
+ 4 9 + 4
38370
Pre-reformer
100% conversion
+ 3 7 + 3
19530
Pre-reformer
100% conversion
+ 2 5 + 2
-2440
Pre-reformer
100% conversion
+ 3 +
-206310
Pre-reformer
UniSim
+ +
-41200
+ + 3
206310
Pre-reformer,
SMR,
WGS
SMR
UniSim, Rate
equations*
Rate
equations*
No.
Reaction
165110
+ 2 + 4
1
-283150
10
+
2
1
-242000
11
+
2
12
-802910
+ 2 +
7
-1428800
13
+ 2 + 3
2
14
-2658850
+ 5 3 + 4
13
-2650470
15
+ 4 + 5
2
16
-3274310
+ 8 5 + 6
19
-3889320
17
+ 6 + 7
2
* The rate equations are based on literature data summarised in Table 6-2.
9
Pre-reformer
Pre-reformer
Basis for Reactor

Design/ Kinetic Data
100% conversion
100% conversion
Location
SMR
Rate equations*
Furnace
Total combustion
Furnace
Total combustion
Furnace
Total combustion
Furnace
Total combustion
Furnace
Total combustion
Furnace
Total combustion
Furnace
Total combustion
Furnace
Total combustion
Main assumptions
For the reactions taking place in the SMR tubes and the WGS reactors, the mixture was assumed to behave like an
ideal gas. This can introduce errors in the mass and energy flows as the gas is very unlikely to behave like an ideal gas
as the pressures inside these reactors are very high (25bar). The Peng-Robinson fluid package was used for the prereformer, which should not introduce significant error as the pressure is elevated.
The viscosity of mixtures for the reactions taking place in the SMR and WGS was assumed to be equal to the mass
average of the viscosities of the individual components. This should not introduce high error, as the pressure drop is
very small in the SMR tubes due to the low velocities.
Heats of Reaction
Heats of Reactions in Design 1 and 2 were calculated at 298K by:
=
Eq. 10
26
GROUP 1

Volume 1
In order to model the change in heat of reaction with temperature the following equation is implemented:
() = () +
Eq. 11
The specific heat capacities are obtained from Sinnott. [56]

() = + + +
Eq. 12
Rates of Reaction
The kinetic data obtained for SMR was based on various sources. All sources were in agreement as the SMR process
is a well known process. The kinetic data for the WGS is vastly dependent on the type of catalyst used. Therefore,
the kinetic data might not be the most accurate as finding sources (for comparison purposes) that used exactly the
same catalyst was challenging. The rates of the reactions 7-9 summarised in table 6-1 are described in the table
below:
Table 6-2: Rates of Reaction in Design 1
Rate
Location
(
.
SMR[57-59]
(
.
With = 1 +
=
=
+ +
HWGS[60]
(1
With = 1 + 10 ( +
LWGS[60]
The parameters used in the equations from Table 6-2 are summarised in Table 6-3.
Table 6-3: Pre-exponential factors and Equilibrium Constants in Design 1
Pre-exponential factor, k
Equilibrium constant, K
67100
4400
= 1.96 10 (
)
= (
4.036)
240100
= 4.23 10 (
)
243900
= 1.02 10 (
)
11000
= 10 .
3600 exp (
)
= 60 1000 exp (
29364
40.32
+
)
1.987 1.987
26830
= 1.0267 (
+ 30.114)
Location
SMR[57-59]
4577.8
= exp (
4.33)
HWGS[60]
4577.8
= exp (
4.33)
LWGS[60]
27
GROUP 1

Volume 1
Table 6-4: Adsorption Constants in Design 1

SMR[57-59]
38300
= 6.67 10 exp(
)
=0
82900
= 6.12 10 exp (
)
70700
= 8.23 10 exp (
)
88700
= 1.77 10 exp (
)
Units
bar-1
[-]
LWGS[60]
=0
bar-1
bar-1
[-]
Units
Pa-1
12542
18.45
= exp (
)
1.987 1.987
=0
Pa-1
3064
6.74
= exp (
)
1.987 1.987
6216
12.77
= exp (
+
)
1.987 1.987
Pa-1
Pa-1
Pa-1
6.1.2 Separations
Desulphurisation
Sulphur removal reaction using iron oxide adsorption [20]:
1
1
() + () () + ()
3
3
= 22 25 1
Eq. 13
This reaction performs better at room temperature, otherwise the iron oxide complex is dehydrated which reduces
the reaction rate and increases difficulty of regeneration. The regeneration reaction is shown below for reference:
1
1
1
() + () () + ()
3
2
3
= 198 25 1
Eq. 14
For short cut design, [16] provides a step-by-step short cut design for desulphurization, however the equations used
are entirely empirical. Therefore, the sulphur loading (mass of sulphur adsorbed per mass of adsorbent) equation
[61] was used to recalculate the breakthrough time based on dimensions calculated from[16].
,
Eq. 15
Where VH2S is the volumetric rate of feed stream [m3 s-1], tb is the breakthrough time [s], CA,in is the H2S concentration
[mol m-3], MWS is the molecular weight of elemental sulphur and Wfb the adsorbent loading in the reactor [g]. Using
experimental data from [61] for sulphur loading (23.29% on average), the check-through method yielded a ~8%
difference in results for breakthrough time which was taken as satisfactory.
PSA
=
Reference [62] explains the short-cut method employed in PSA design. In essence there are 4 mole balance
equations and a product recovery equation that govern the 4 step PSA cycle. The 4 step PSA cycle is then
extrapolated to an 11 step cycle with 3 pressure equalization stages to improve recovery. A critical assumption is
that the feed gas is a binary mixture of 80% H2 and 20% CO2. The previous process section (SMR-WGS) provides a
feed that is 78% H2 and 22% CO2 with negligible amounts of other gases, therefore it was decided that the
preliminary assumption was valid. Using the relevant isotherms from [63] shown below in Figures 6-1 and 6-2, along
with operating conditions of 25 bar(a) and 30C, inlet flowrates, the stated 4 mole balance equations, recovery
equation and suggested PSA cycle schedule (Table 6-5), the required dimensions of the PSA column were obtained.
28
GROUP 1

Figure 6-1: PSA Adsorption Isotherm [63]
Volume 1
Figure 6-2: PSA Adsorption Isotherm [63]
Table 6-5: PSA cycles
For PSA design, the constants will be explained before the main equations.
Constant i (ratio of hold-up component i in void space as fraction of total hold-up):
=
1
1
1+
Eq. 16
Where is the void fraction of the bed [-] and Ki represents the adsorption equilibrium constant or isotherm slope [-]
The method at which Ki is calculated in the case of KCO2 for example:
Eq. 17
29
GROUP 1

Volume 1
Where XCO2 is the amount of component CO2 adsorbed per kg of adsorbent, p is the density of adsorbent [kg m-3],
PCO2 is the partial pressure of CO2 [Pa], R is the gas constant [J mol-1 K-1] and T is the operating temperature at 303
[K]. The process is repeated for H2.
Constant i (alternate expression to express the impact of adsorbent-adsorbate interactions on PSA performance):
= ( , , ) = 1 +
( )
Although complicated,
( )
Eq. 18
simply represents the gradient of the chord between two points on the
isotherm graph and PH is the adsorption pressure [Pa]. This means that i = i for linear isotherms. For clean beds,
the value of the first point in the calculation of i is (0,0).
The moles required for the feed step:

Eq. 19
Where Qin is the inlet feed flowrate [mol s-1], tfeed is the feed step time [s], Pratio is the ratio between the adsorption
and desorption pressure of the adsorption column [-] and is a constant as defined by [62]
The moles required for the purge step:

Where tPU is the purge time of the cycle [s]. The ratio
Eq. 20
=
is equal to 1 for clean beds.
The moles of pure, light product withdrawn during the feed step:
1 + ( 1)
Eq. 21
Where Qout is the outlet flowrate [mol s-1], is the selectivity parameter [-] which is the ratio of CO2 to H2 and yCO2F
is the mole fraction of CO2 if the feed [-]
The pressurization with product step:
= [
1]
Eq. 22
Where tPR is the time of product recovery (re-pressurisation) [s] and 0 is the ratio of CO2 to H2 [-].
Recovery of the light component for this 4 step cycle using pressurization by product:
=
Eq. 23
Where Rb is the recovery of the H2product [-] and yH2F is the mole fraction of the H2 in the feed [-].
Constant (used to determine column dimensions):
[] =
[ ][] []

[]

Eq. 24
Where ACS is the cross-sectional area of the bed [m2], L is the bed length [m], PL is the desorption pressure of the
column [Pa], CO20 which equals CO2 if the purge gas is presumed to be pure [-] and T the operating temperature of
the column [K].
30
GROUP 1

Volume 1
MEA
Monoethanolamine (MEA) is a primary amine with two hydrogen atoms attached to the nitrogen atom, and is used
to absorb CO2 from a flue gas stream. This absorption is classified as a chemical absorption, as opposed to a physical
absorption due to the equilibrium reactions taking place between the MEA and the CO2, the details of which are
given below [64]:
1. Ionization of water
2 +
Eq. 25
2. Hydrolysis and Ionization of dissolved CO2

+ 2 +
Eq. 26
+ +
Eq. 27
3. Dissociation of bicarbonate
4. Dissociation of MEAH+
( ) + + ()
Eq. 28
5. MEACOO- (carbamate) reversion to bicarbonate

( ) + () +
Eq. 29
6. to model the MEA absorption process, equilibrium data is used to estimate the required amount of MEA to
In order
be fed into the absorption column based on the partial pressure of CO2 in the flue gas. Figure 6-3 shows the
relationship between CO2 feed partial pressure and the loading CO2 using 30 wt% MEA solution.
Figure 6-3: CO2 loading as a function of its partial pressure [65]

The circles represent the system at 40 C. The CO2 partial pressure is 58 kPa so the corresponding loading is 0.6
moles of CO2 per mole of MEA.
This value of 0.6 moles of CO2 per mole of MEA is applicable because the feed gas to the absorber is specified to be
at 40 C and using 30 wt% solution. However, this data relies on the assumption that equilibrium conditions are
achieved within the absorber, an ideal case which is unlikely to be achieved in reality. In practice, more MEA will be
required to achieve the same level of absorption of CO2. To account for this, it is assumed that 80 % of the
equilibrium value will be achieved:
0.6
0.48
0.8 =

Eq. 30
31
GROUP 1
6.2

Volume 1
Design 2
6.2.1 Reactions
All reactions taking place is reactors in Design 2 are summarised in the table below:
Table 6-6: Reactions in Design 2
no.
Reaction
Hrx (298K)
(J/mol)
Location
Basis for Reactor

Design/ Kinetic Data
+ 6 13 + 6
79600
Pre-reformer
100% conversion
+ 5 11 + 5
59210
Pre-reformer
100% conversion
+ 4 9 + 4
38370
Pre-reformer
100% conversion
+ 3 7 + 3
19530
Pre-reformer
100% conversion
+ 2 5 + 2
-2440
Pre-reformer
100% conversion
+ 3 +
-206310
Pre-reformer
UniSim
+ +
-41200
Pre-reformer &
SMR
UniSim, Rate equations*
+ + 3
206310
SMR
Rate equations*
+ 2 + 4
165110
SMR
Rate equations*
10
0.5 +
-938200
Air reactor
Rate equations*[66]
11
+ + 2 +
-35800
Fuel reactor
Rate equations*[67]
12
+ +
-242000
Fuel reactor
Rate equations*[67]
13
+ +
-283000
Fuel reactor
Rate equations*[67]
* The rate equations are based on literature data summarised in tables 6-2 and 6-7
Table 6-7: Kinetic data for CLC

Rate (kmol/m3s)
k (s-1)
K(/)
Air Reactor[66]
Where CA=0.349kmol/m3
= 0.00067
Fuel Reactor[67]
2366
= 1.3 10 exp (
)
26500
= 9.4 10 exp (
)
= 0.0063
26410
= 1.3 exp (
)
= 0.003
Where =30
32
GROUP 1

Volume 1
Main assumptions:
There are more than three reactions in the fuel reactor; however, the combustion reactions for higher alkanes were
not considered for simplification purposes. In addition to that, the fuel and air reaction for CL were assumed to be
isothermal for simplification purposes. This is because the heat carried by the nickel carriers introduced a lot of
complications in the modelling of the temperature changes. These assumptions could impact the design significantly
as the heats of reactions are relatively big.
For the reactions taking place in the SMR tubes and the CL reactors, the mixture was assumed to behave like an ideal
gas. This can introduce errors in the mass and energy flows as the gas is very unlikely to behave like an ideal gas as
the pressures inside these reactors are very high (25bar). The Peng-Robinson fluid package was used for the prereformer which should not introduce significant error as the pressure is elevated.
The viscosity of mixtures for the reactions taking place in the SMR was assumed to be equal to the mass average of
the viscosities of the individual components. This should not introduce high error, as the pressure drop is very small
in the SMR tubes due to the low velocities.
The kinetics for the reactions taking place in the CLC reactor can be found in table 6-7. While the kinetics for the
reactions taking place in the SMR are summarised in table 6-2.
The heat of reactions and specific heat capacities are calculated in a similar way as in design 1 (eq.12-14).
The kinetic data obtained for SMR was based on various sources. All sources were in agreement as the SMR process
is a well-known process. However, the kinetic data for the CL reactors can be less accurate as there are a limited
amount of papers that provided kinetic data for CL as it is a relatively new process. Therefore, there is a higher
degree of uncertainty for the results obtained for this process.
6.2.2 Separations
Membrane separation in SMR
In the SMR tubes the hydrogen flows through the membranes with the following molar flux (kmol/m2 h) [57-59, 68]
296 10
Eq. 31
.
.
=
( ,
,
)
Where pi is the partial pressure (bar) and is the membrane thickness (m).
Desulphurisation
The same desulphurisation process is used as in design 1 (see section 6.1.2).
33
GROUP 1

Volume 1
Hazards and Safety
7.1 Chemical Hazards

It is necessary to know hazardous information of all the chemicals associated with the plant to ensure safe operation. This is summarised below in Table 7-1 with reference
to the Material Safety Data Sheets (MSDS) approved by the Health and Safety Executive (HSE).
Table 7-1: Hazardous information process chemicals
Components
Type
[69]
Activated carbon
TWA
Aluminium oxide[B][C]
TWA
Butane[70]
TWA
Carbon[C]
TWA
Carbon dioxide
TWA
Carbon monoxide [71]
TWA
Caesium carbonate[D]
TWA
Chromium (III) oxide[C]

Chromium (VI) oxide[C]
TWA
TWA
Copper (II) oxide
TWA
Ethane[72]
TWA
Hexane
TWA
Hydrogen[73]
Hydrogen sulphide[74]
TWA
Exposure Limits
Concentration
10 mg/m3 (Total inhalable dust)
4 mg/m3 (Respirable dust)
600 ppm
750 ppm
3
3.5 mg/m (Total inhalable dust)
5,000 ppm
9150 mg/m3
15,000 ppm
27,400
3 3
30 ppm
35mg/m
mg/m
200 ppm
232 mg/m3
3
10 mg/m (Total inhalable dust)
0.5 mg/m3
0.005 mg/m3
0.2 mg/m3 (Fume)
1 mg/m3 (Dust and mist)
1,000 ppm
20 ppm
72 mg/m
5 ppm
10 ppm
Duration
Flammability/Explosive Limits
Lower
Upper
8 hours
8 hours
Not flammable, nor explosive
8 hours
15 mins
8 hours
8 hours
15 mins
8 hours
15 mins
Toxicological Information
Results
Dose
Duration
Oral LD50
2,000 mg/kg
Inhalation LD50
8.5 mg/L
1 hour
-
1.40%
9.40%
Inhalation LC50
658 mg/L
4 hours
(50 g/m3)
Oral LD50
8,000 mg/kg
Extremely flammable
(12.5%)
(74%)
Inhalation LC50
1,300 ppm
4 hours
8 hours
Oral LD50
2,333 mg/kg
8 hours
8 hours
Oral LD50
80 mg/kg
8 hours
Oral LD50
470 mg/kg
Inhalation LC50
Oral LD50
Inhalation LC50
1.443 mg/L
25 g/kg
48,000 ppm
-
0.25 hours
4 hours
Inhalation LC50
356 ppm
4 hours
8 hours
2.40%
16%
8 hours
1.20%
8.30%
4%
77%
3.90%
45.50%
8 hours
15 mins
34
GROUP 1
Iron (III) oxide[C]
TWA
Methane[75]

3
5 mg/m (Fume)
8 hours
10 mg/m3 (Fume)
15 mins
4.40%
15%
3
1 ppm
7.6 mg/m
8 hours
3.40%
27%
3 ppm
15 mg/m3
15 mins
Volume 1
Inhalation LC50
Oral LD50
Inhalation LC50
Dermal LD50
Pentane[81]
TWA
600 ppm
8 hours
1.10%
7.80%
Oral LD50
Inhalation LC50
5,396,000 ppm
1,089 mg/kg
1,487 mg/m3
2,504 mg/kg
0.46 ppm
0.16 ppm
11,000 mg/kg
50 mg/kg
2,000 mg/kg
25.3 mg/L
Propane[82]
TWA
10.8%
Inhalation LC50
800,000 ppm
TWA
8 hours
15 mins
8 hours
8 hours
8 hours
1.7%
Silica[A]
1,000 ppm
1,250 ppm
0.05 mg/m3
3
5 mg/m (Fume)
10 mg/m3 (Fume)
Monoethanolamine
(MEA)[76]
TWA
Nickel[77]
TWA
1 mg/m3
8 hours
Inhalation LC50
Nickel (II) oxide[78]
TWA
0.5 mg/m3
8 hours
Oral LD50
Dermal LD50
Nitrogen[79]
Oxygen[80]
[83]
Sulphur
TWA
Water
Zinc oxide[84]
where:
Note:
TWA
TWA
Flammability/Explosive limits
LD50
LC50
[A]
[B]
[C]
[D]

35 g/m
400 g/m
0.25 hours
Oral LD50

8 hours
2 hours
4 hours
10 mins
1 hour
-
5,000 mg/kg
Oral LD50
10,000 mg/kg
15 mins
Work place exposure limit expressed as time weighted average

Percentage of gas or vapour in air capable of causing a fire or explosion in the presence of an ignition source
Lethal dose at which 50% of population is killed in a given period of time
Lethal concentration required to kill 50% of population
Component of Sulfatreat catalyst used in desulphurisation
Component of catalyst used in SMR
Component of catalyst used in high temperature water gas shift
Component of catalyst used in low temperature water gas shift
35
GROUP 1

Volume 1
7.2 Process Hazards

Each section of the plant is designed by bearing in mind the hazardous chemicals they are processing. Potential
hazards are identified in this section, with appropriate precautions suggested.
7.2.1 General Plant Hazard
In both proposed designs, many pieces of equipment require the use of catalysts including the desulphurisation
columns, pre-reformer reactor, water gas shifters, PSA unit and chemical looping combustion reactors. Changing of
the catalyst beds can be a potential risk to personnel if the catalysts are not handled properly. For example, in the
desulphurisation unit, the catalyst bed weighs 15 tonnes and so careful operation of lifting equipment is required.
Personnel are also advised to wear PPE to protect themselves from exposure to hazardous catalysts with the
potential to cause chronic illness.
Nitrogen is used throughout the plant for purging the equipment during maintenance and start-up. Nitrogen can be
a potential risk to operating personnel if they are exposed to nitrogen-rich atmosphere without self-contained
breathing apparatus. According to the material safety data sheet, nitrogen may cause asphyxiation at high
concentrations while the victim is unaware of the situation. Symptoms include loss of mobility and consciousness.
7.2.2 Desulphurisation Unit
There are no significant process hazards or safety problems present in this section. Operating temperature of the
column is at 30oC using Sulfatreat as a catalyst. However, if the zinc oxide variant (Katalco 32 5) is used instead, a hot
bed is required at a much higher temperature, around 400oC. Operating personnel must allow the catalyst bed to be
fully cooled down and be extra cautious when draining and reloading the bed.
7.2.3 Furnace
The furnace is operating at an extremely high temperature to provide energy for the Steam Methane Reformer
reaction and for pre-heating purposes of other process streams. A ratio of 1.1 excess air to fuel is fed into the
furnace to ensure complete combustion of the fuel gas. However, if incomplete combustion occurs carbon monoxide
will be produced, endangering the personnel responsible for flue gas sampling. Suffocation can occur if they are not
wearing appropriate PPE. Moreover, the fuel gas line and the furnace wall should be inspected regularly. Any
abnormal temperatures or pressures must be reported with an emergency shutdown initiated if necessary.
7.2.4 Pre-Reformer, Steam Methane Reformer (SMR)
Both the pre-reformer and SMR operate at around 30 bar(a) and at high temperatures, 400 oC and 950oC
respectively. Proper heat-insulated protection gear must be worn when going near the reactors. Both reformers use
a nickel catalyst. This catalyst shall not be exposed to gases containing carbon monoxide at temperatures lower than
200oC, to avoid the formation of nickel carbonyl - an extremely dangerous substance causing organ failure and death
a few days after inhalation. This situation is however, very unlikely. Both reformers require an input of high
temperature compressed steam. The steam line needs to be checked regularly for leaks to ensure safe operation.
7.2.5 Water Gas Shifters
The catalysts used in both high temperature and low temperature water gas shifters are pyrophoric in nature, which
means any air or water exposure should be avoided. The risk of an exothermic reaction is greatest during a plant
shutdown when plant pressure is near or at atmospheric. In the case of a fire caused by the exothermic reaction,
Class D fire extinguishers should be used following the safety instructions provided by the catalyst vendor.
7.2.6 PSA Unit
This section contains mostly hydrogen as its feed and product, it should therefore be stand-alone and kept away
from heat, hot surfaces, sparks, open flames and other ignition sources. The minimum amount of hydrogen gas is
compressed and stored if need be in a well-ventilated area, the storage should be monitored by experienced staff to
eliminate any potential human errors. Gas leak inspections should be carried out on a regular basis with immediate
section shutdown to fix the leak. In case of a fire, do not extinguish unless the leak can be stopped safely due to the
possibility of an uncontrolled explosive re-ignition. It is suggested in the MSDS that the containers should be kept
cool by spraying water continuously from a protected position in case of an accident.
36
GROUP 1

Volume 1
7.2.7 MEA Carbon Capture Unit
There are two major hazards for the MEA process; one is the handling of MEA solution, the other is the potential
leakage of high purity carbon dioxide. MEA is a very corrosive substance according to the MSDS, causing serious
chemical burns and damage to the respiratory tract if inhaled. PPE and compulsory training are required for
operating personnel to safely handle MEA solution. A well-ventilated system is also required. Regular inspections
need to be carried out on the pipelines, absorption and stripping columns.
According to the MSDS, carbon dioxide stimulates respiration at a low concentration, it then causes respiratory
depression as the concentration increases in air. Prolonged exposure to high concentrations can result in narcosis
and even death from asphyxiation. It is therefore crucial to have ventilation systems, alarms and gas detectors
installed to mitigate the situation when there if a carbon dioxide leakage.
7.2.8 Chemical Looping Combustion Reactors
Chemical Looping Combustion reactors use nickel and nickel oxide particles as oxygen carriers. In the design they are
transported in a closed looping system which minimises the risk of release. In the case of an emergency, a filter is
present to prevent nickel oxide particles escaping through the pressure relief valve. Additional care must be taken
when replacing Ni/NiO particles in the reactors, full PPE must be worn. Careful monitoring of reactor temperature is
essential to prevent reactors from overheating and melting the membrane tubes. A trip system attaches the reactor
temperature indicators to the flow ratio controller to terminate inlet flow if necessary.
7.2.9
Hazards Ranking
Table 7-2: Hazard ranking
Number
1.
Potential Risk
Changing of catalyst beds
2.
Leakage of nitrogen
during purging pipelines
and equipment
Incomplete combustion
in the furnace or the fuel
reactor of chemical
looping
Leakage of extremely hot
flue gas from furnace
3.
4.
5.
Leakage in the fuel line
6.
7.
Release of high pressure,

high temperature steam
Leaks in the PSA system
8.
Exposure to MEA
9.
Temperature fluctuation
in the CLC reactors
Outcome
Physical injury to personnel,
chronic diseases if exposed to
catalysts above the safe limit
Asphyxiation, loss of
consciousness, death
Production of unwanted
carbon monoxide, causing
injury or suffocation to
personnel if leaked
Serious burns
Fire or explosion, physical

injury to personnel in case of
inhalation
Burns and injury to personnel
Fire or explosion due to
hydrogen rich atmosphere
Chemical burns, irritation to

respiratory system, chronic
diseases
Overheating above 500oC
would cause the SMR
membrane tubes to melt
Mitigation
Make use of dump trucks and lifting
equipment such as cranes; PPE must be
worn
Venting systems; alarms and gas
detectors should be installed, evacuation
required in case of emergencies
Venting systems; alarms and gas
detectors should be installed, evacuation
required in case of emergencies
Proper monitor and control of abnormal
pressure and temperature; PPE must be
worn; immediate shutdown allowing the
furnace to cool before carrying out
inspection
Alarms and gas detectors should be
installed; inspections carried out regularly
in the fuel line; PPE such as masks
PPE; regular inspection and maintenance
of steam line
Gas leak inspections should be carried
out regularly; any ignition source is
inhibited around the area; emergency
response teams (ERT) present during
leaks/change out
Venting systems; PPE must be worn; staff
training; check for leakages regularly
Trip system installed to terminate flow
immediately; staff training to deal with
equipment overheating
37
GROUP 1
10.
11.
12.

Volume 1
Exposure to nickel or
Chronic illness, cancers, death
Mask protection to avoid inhalation of
nickel compounds
nickel powders; PPE such as gloves
should always be worn when handling
nickel compounds
Dust explosion
Injury to personnel, death
Dusts or powders from potentially
flammable/explosive compounds such as
nickel and carbon should keep away from
potential ignition source; use of wet
sprays to limit dust in air; avoid using
vacuum cleaner
Noise
Damage to ear-drum,
PPE such as ear mufflers should be worn
permanent damage to hearing
Table 7-3: Hazard and Risk Safety Sheet
38
GROUP 1

Volume 1
Environmental Impact
The material inventory list for Design 1 is presented in Table 8-1 below.
Table 8-1: Design 1 Material inventory list
Section /
[Equipment]
Material or
Waste
Held inventory
[tonne]
1 / [T-101
A/B]
Sulfatreat 410
CHP
(Iron oxide)
29.4 tonnes in service

14.7 tonnes in reserve
(1 columns worth)
2 / [R-201]
2 / [R-202]
2 / [R-203]
2 / [R-204]
3 / [T-301306]
Release likelihood
Release quantity
[tonne yr-1]
Environmental impact
Non-hazardous
[85], [86]
1. No release hazards
in storage
2. Bed change once
per year
~14.7 tonnes per

year
Safe for landfill disposal with no

significant effects to environment.
EWC code: 05-01-16
Nickel catalyst
(PRICAT 9920)
8 tonnes in service
with 8 tonnes in
reserve
Slightly-hazardous
Spent material may be
hazardous but can be
recycled [87]
in storage
2. Estimated change
out in 4 years
1. 8 tonnes at the
end of service life
(4 years)
Nickel catalyst
(PRICAT 9920)
35 tonnes in service
with no additional
inventory
Slightly-hazardous
Spent material may be
hazardous but can be
recycled [87]
in storage
2. Estimated change
out in 4 years
1. 35 tonnes at the
end of service life (4
years)

with no additional
inventory
Slightly-hazardous
May be toxic to aquatic
life [88]

with no additional
inventory
Slightly-hazardous
Product contains zinc
oxide which is classified as
toxic to aquatic bodies[89]

12.34 tonnes in
reserve
(1 columns worth)
Non-hazardous
[90]
in storage
1. Estimated change
out in 4 years
in storage
2. Estimated change
out in 4 years
in storage
2. Estimated changeout of 1 column
per 1.5 years
1. 7.02 tonnes at
the end of
service life (4
years)
1. 7.39 tonnes at
the end of
service life (4
years)
Change-out not
specified, ~12.34
tonnes per 1.5 years
for single column
change-out
Iron-chrome
HWGS catalyst
(HiFUEL
W210)
LK-823
copper/zinc
(LWGS
catalyst)
Norit R2030
Activated
carbon
Hazard description with

respect to environment
Safe for landfill but spent material

may require disposal in containers
to prevent contact with water
bodies.
EWC code: 16-08-02*
may require disposal in containers
to prevent contact with water
bodies.
EWC code: 16-08-02*
Safe for landfill but has to be
stored in containers. Harmful to
aquatic life.
EWC code: 16-08-02*
Safe for landfill but has to be
stored in containers. Harmful to
aquatic life.
EWC code: 16-08-02*
Safe for landfill disposal with no
significant effects to environment.
EWC code: 05-07-99
39
GROUP 1
4 / [T-403]
4 / [V-403]

Flue gas
Mole fraction:
1.38% CO2
94.2% N2
2.12% H20
2.26% O2
1.78 ppm (vol)
MEA
MEA
NA
75 tonnes of MEA in
reserve (30 % of surge
drum volume for make
up to full drum volume
of 30 wt% solution)
In service: 183 tonnes
per hour of MEA
circulating in MEA
system
Non-hazardous
1. MEA disposal limits at
about 6 [mg m-3]
TWA8 OSHA [91]
2. Other gases not
hazardous to health
3. Greenhouse gas
emissions discussed
further on
1. Fixed quantity
released per hour
2. Within emission
boundaries (6 ppm
wt STEL; ours is
1.78 ppm vol or
3.87 ppm wt)
Hazardous [91]
1. Toxic to aquatic life
2. Safety hazard
3. Additional disposal
considerations
required
1. No real fixed
quantity release
2. No accidental
release should
occur if proper
procedures are
followed
Volume 1
~0.126 ktonne/hr or
~1008 ktonne/year
total flue gas release
~0.49 kg/hr or 3920
kg/yr MEA release
~2742 kg/hr or 21.9
ktonne/yr CO2
release
Estimated to be 0
tonnes per year with
the exception of end
of life change outs
Safe for release to atmosphere but

if MEA concentration increases to
6 [mg m-3], there are potential
health and environmental issues.
No EWC code.
Highly toxic to aquatic bodies and

subsequent wildlife. Unused MEA
preferably sent to incinerator
while spent MEA sent for
reprocessing or pre-treatment
before disposal.
EWC code: 07-01-01*
40
GROUP 1

Table 8-2: Design 2 Material inventory list
Section /
[Equipment]
Material or
Waste
1 / [T-101
A/B]
Sulfatreat 410
CHP
Nickel
catalyst
(PRICAT 9920)
2 / [R-201]
2 / [R-202]
2 / [R-203]
2 / [R-202]
2 / [C-201]
Nickel
catalyst
(PRICAT 9920)
Held
inventory
[tonne]
Same as
design 1
Same as
design 1
85.7 tonnes
in service
with no
additional
inventory
Nickel
~10 tonnes
oxidised in
service
Nickel Oxide
~10 tonnes
reduced in
service
Cyclone flue
gas.
Mole
fraction:
~100% N2
NA
Hazard description with respect to

environment
Volume 1
Release likelihood
Release quantity
[tonne yr-1]
Environmental impact
Same as design 1
1. Same as design 1
Same as design 1
Same as design 1
Same as design 1
1. Same as design 1
Same as design 1
Same as design 1
Slightly-hazardous
Spent material may be hazardous
but can be recycled [87]
in storage
2. Estimated change
out in 4 years
85.7 tonnes at
the end of service
life (4 years)

may require disposal in containers to
prevent contact with water bodies.
EWC code: 16-08-02*
~10 tonnes per

operation cycle
Safe for landfill disposal but

recommended being recycled.
EWC code: 16-08-02*
~10 tonnes per

operation cycle
Safe for landfill disposal but

recommended being recycled.
EWC code: 16-08-02*
~ 0.03 ktonnes
per hour
~ 245 ktonnes per
year
May cause oxygen deprived

atmosphere around release area,
recommended to be mixed with air
before release.
Non-hazardous[92]
Non-hazardous[93]
Slightly-hazardous
1. May cause an oxygen deprived
atmosphere surrounding the
release area
2. Can be solved with air mixing
before release to reach safe
conditions
1. Scheduled
regeneration once
attrition rates are
severe
in storage
1. Scheduled
regeneration once
attrition rates are
severe
in storage
1. Steady release into

atmosphere per
hour
41
GROUP 1

Volume 1
8.1 General
The six digit EWC code corresponds to the European Waste Catalogues classification of waste [94]. Six digit codes
that end with * are considered active/hazardous waste and additional steps should be carried out to dispose of it.
This plant would be classified under Section 5: Wastes from Petroleum Refining, Natural Gas Purification and
Pyrolytic Treatment of Coal but spent catalysts would be under Section 16: Wastes not otherwise specified in the list.
Although there is no difference between the 2002 EWC and the current EWC, [95] is the most up to date website. In
relation to regulations in the UK, [96] was used to re-check the EWC classifications and were found to be similar. In
terms of importance (priority), flue gas treatment and release should be discussed followed by solid and liquid waste
treatment options.
8.2 Flue gas treatment and disposal
Following table 8-1, only CO2 and vaporized MEA will be discussed in terms of disposal and treatment. Note that the
MEA has already been pre-treated prior to removal via water present in the cooled stream (26a) and the MEA
released is due to the remaining water present in the stack. MEA is considered hazardous to aquatic life with a
minimum toxicity limit of 33 [mg L-1] with a TWA8 OSHA limit of 6 [mg m-3] [91]. Calculations were completed to
determine the maximum concentration of MEA (~0.14 [g s-1]) downstream using a designed stack height of 80 [m]
(Appendix B: Environmental impact sample calculations). The results show that the maximum concentration lies 200
[m] downstream of the plant with a concentration of 0.09 [mg m-3]. Due to the lack of information regarding MEA
emission rates in flue gas, it is not possible to state whether or not this 0.09 [mg m -3] is above or below allowed
limits. Note that this does not take into account the fact that MEA is highly soluble in water and may condense much
closer to the stack. Should further reduction be required, the stack could be re-designed to periodically inject water
vapor at different heights to ensure that more MEA condenses before reaching the top. Additionally, MEA does not
persist in the environment and trace emissions should be viable so long as the plant is not situated near any large
aquatic bodies.
In Design 1, CO2 is released at a rate of 21.9 kt yr-1. Through the use of MEA carbon capture, the plant is already
using the BAT (Best Available Technique) based on the process selection employed. Although not a hazardous gas,
the European Union Emission Trading Scheme (EU ETS) was put in place to reduce CO2 emissions as a way to combat
climate change due to greenhouse gas effects. Following the reference document provided [97], H2 production has
an allocated 8.85 allowances per tonne of product produced (1 allowance = 1 tonne of CO2 free release). Taking into
account the estimated decrease in free allocation by 2019 [97], this value comes to ~3.27 allowances per tonne
product or ~131476 allowances per year of operation (Appendix B: Environmental impact sample calculations).
However, the plant will only use ~21900 allowances based on the flue gas release and the remainder of that
(~109576 allowances) will be sold on the carbon market. The price per allowance fluctuates greatly and depending
on which side of an argument one takes, it can range from a pessimistic ~5.5 per allowance [98] or an optimistic
~13.3 per allowance [99] in the year 2020. Taking an in-between value of 10, the allowances (if all auctioned) will
net the plant an additional ~1 million a year. Finally, it is worthwhile to note that the UK carbon floor standards
were not taken into account as the EU ETS represents a more stable foundation to base off CO2 release.
In Design 2, no greenhouse gases are released due to the assumptions made regarding nitrogen in the chemical
looping system (negligible NOx). Should this be the case, pure N2 gas will be released to the atmosphere at a rate of ~
245 [kt yr-1]. Although there are no known laws with regards to nitrogen release, this release rate may cause an
oxygen deprived atmosphere surrounding the plant stack which could endanger flight based wildlife. The simplest
option that would allow safer release of the chemical looping flue gas would be to simply feed air through the stack
so that the oxygen levels at the point of release are satisfactory. However, it is worthwhile to consider selling the
pure N2 from the stack but it is beyond the scope of this plant. Additionally, the full ~131476 carbon allowances will
still be allocated to the H2 plant which should net an additional profit of ~1.3 million a year.
Although mentioned in the earlier sections, it was assumed that there is no significant production of NOx for either
design. This was considered valid for Design 1 as the Furnace operates at temperatures (507C) lower than thermal
NOx formation (1600C) and proper composition control for the Furnace inlet gas would reduce the amount of fuel
NOx formed. In addition, chemical looping combustion in Design 2 is inherently a low NOX producer.
42
GROUP 1

Volume 1
8.3 Solid waste disposal

Following tables 8-1 and 8-2, both the desulphurisation and PSA sections have relatively inert materials with
significant disposal quantities per year of operation. Although safe for landfill, spent Sulfatreat may be recycled and
used as additional material in road construction, bricks and sand stabilizers [21] while spent activated carbon may be
reactivated or used as fuel in fire cement kilns [100]. Excluding charges for transport and landfill site gate tax, EWC
codes: 05-01-16 and 05-07-99 should be classified under inert wastes in the Scottish landfill tax scheme [101] and
charged at 2.60 per tonne.
Spent reactor catalysts are not replaced as often as the desulphurization adsorbents used in desulphurization and
PSA. However, they are classified as active/hazardous substances due to the presence of a transitional metal (EG:
Nickel) under the EWC. Recycling is usually preferable to landfill disposal partly to recover the expensive metals
present (Palladium in Design 2) but also due to the high tax incurred for active materials. Under the Scottish landfill
tax scheme, EWC codes: 16-08-02* should fall under the active wastes classification and charged at 82.60 per
tonne. Catalyst recycling companies such as Globe Metal and Gulf Chemical could be used to deal with the spent
catalysts.
8.4 Liquid waste disposal
MEA is the only liquid waste material besides water in both of the designs. Due to the long life of MEA during
operation, it is rare that large quantities of MEA will have to be disposed of. However, spent MEA would fall under
the active waste classification per the Scottish landfill tax scheme and would be charged 82.60 per tonne upon
disposal.
The water usage for both designs are significant but 99.99% of the process water will be recycled and reused via
various water knockout drums throughout the plant. At steady state operation Design 1 requires an additional input
of ~9 tonnes per hour of water and subsequently Design 2 requires ~19 tonnes per hour of water. Cooling water
requirements will depend on the further analysis of the Heat exchanger network and will be discussed in the critical
review.
43
GROUP 1

Volume 1
Economic Analysis of the Two Designs
9.1 Introduction and Assumptions

This section presents an economic analysis of the two designs. The profitability of the two designs will be compared
and a recommendation made, based upon the calculated results. Before the analysis is conducted, it is important to
note that a significant number of assumptions were made and are highlighted below:
1. Investment: In order to provide the funds required for capital investment into the project, Costain should
retrieve a loan from a bank or investors who agree to a 5 % annual interest loan payable over the lifetime of the
project - set to be 20 years. However, to get a better idea of the economic health of the project, the cost of
capital i was set at 10 % for the analysis. This figure is probably higher than would be agreed upon in actuality,
since Costain are a well-established and reputable company; investors would likely be comfortable settling for a
lower return than 10 % from Costain.
2. Construction: It was assumed that it would take two years from time t=0, where the land was purchased, to
plant operation, i.e. in 2018. In other words, during those two years, detailed design of the plant, along with
procurement and installation of the equipment, will have taken place. Furthermore, it was assumed that the
plants output during the first year of its operating life (2018 2019) will be 60 % of the target output, to allow
for initial reliability problems associated with burn-in of equipment. Subsequent years will operate at full
capacity.
3. Inflation: The Chemical Engineering Plant Cost Index (CEPCI) was used to adjust historical prices into the value of
money in 2018. A constant future inflation rate of 2% per annum was estimated for the duration of the project;
this figure was used to adjust the 10% interest rate.
4. Depreciation: This is calculated using a declining balance model. This is explained in Appendix C-5.
5. Feed and Product Prices: By far the largest influence on the profitability of the plant was the estimation for the
price of hydrogen. Essentially, a number of prices for hydrogen were collected from literature [45] and DOE,
2012) and collated together to create a range with a median, mode and expected value. This is explained in
more detail in Appendix C-3. As for the price of the feedstock, natural gas, it was relatively easy to find
consistent, agreeing data describing it and the predicted trend over the next 20 years. While there was also an
appreciable fluctuation of prices found for the by-product CO2, the observed trend was that CO2 was worth
significantly less per tonne than hydrogen; therefore the final effect on the overall profitability of the plant was
not as severe as that of hydrogen.
6. Risk Analysis A rough estimate of the likelihood of Costain to achieve specific net profit margins over the course
of the 20 year project was conducted by estimating p10, p50 and p90 values relating to the estimate of hydrogen
price. This is explained in more detail in Appendix C-3.
7. Capital Cost Estimate: Purchase costs were estimated using general correlations of the form Ce = a + bSn.
Installation costs of the equipment were calculated by multiplying by the relevant Wroth factor; a table of these
is given in Appendix C-1.
8. Operating Cost Estimate: It was assumed the plant runs at 100 % capacity, and the plant attainment is 8000
hr/yr. The price of electrical energy for fluid compression was taken to be 32.50 per GJ of electricity, and
assumed to remain at this value for the next 20 years during the plants operation. As for the cost of cooling
water, a modern-day value of 0.007 /m3 [102] was used. However, it was noted that the cost of cooling water
requirement of both plants were so low compared to the cost of, for example, gas compression or catalyst
replacement, that the cost of cooling was assumed negligible.
9.2 Estimating the Total Capital Cost
Every piece of process equipment within the ISBL/OSBL boundary had either a calculated or estimated purchase
cost. In very general terms, the purchase cost of pumps, compressors and heat exchangers were calculated using
Equation 18 [103]. Towers and vessels were costed using graphical correlations [102] these are included in Appendix
C as Figures C-1 and C-2.
= +
Eq. 32
Where Ce is the purchase cost of the equipment, a, b and n are dimensionless numbers, S is a size rating and the
CEPCI numbers refer to the CEPCI index in 2010 and 2018 respectively.
44
GROUP 1

Volume 1
To calculate the installation cost of each ISBL item, the purchase cost was multiplied by the relevant Wroth Factor.
Wroth factors are an improvement upon Lang facts, in the sense that offer a more complete list. They take into
account the cost of site development, piping, electrical installation, painting, foundations, structures, contractors
fee, engineering, overheads, and supervision [104]. The total ISBL was taken as the sum of the installation costs of
every component within the ISBL limit.
General figures of the OSBL being equal to 50 % of the ISBL, Engineering costs being equal to 20 % of ISBL + OSBL,
and Contingency as being 10 % of ISBL + OSBL were then summed to calculate the partial fixed capital investment
(PFCI). Since the plant is based in the UK, the PCFI was multiplied by the relevant location factor of 1.02 to retrieve
the Fixed Capital Investment (FCI), which was found to be 87.0 million for Design 1 and 56.4 million for Design 2.
Working Capital was assumed to be 10 % of the FCI; adding the Working Capital to the FCI means the Total Capital
Investment could be easily calculated. Calculation steps are highlighted in the Appendix C-1; retrieved results are
highlighted in Table 9-1.
Parameter
ISBL
OSBL
EC
CC
PCI
LF
FCI
WC
TCI
Table 9-1: Calculated steps involved in the estimate of the Total Capital Investment
Value
Definition
Design 1
Design 2
Inside Battery Limits Cost
43.7
28.4
Outside Battery Limits Cost
21.9
14.2
Engineering Costs
13.1
8.51
Contingency Charges
6.56
4.26
Partial Fixed Capital Investment
85.3
55.3
Location Factor
1.02
1.02
Fixed Capital Investment
87.0
56.4
Working Capital
8.70
5.64
Total Capital Investment
95.7
62.1
Unit
M
M
M
M
M
M
M
M
9.3 Estimating the Total Variable Costs

Every plant item which had a definite operating cost associated with it (pumps, compressors, coolers, heaters and
replacing beds inside reactors and columns) had a calculated or estimated annual operating cost. These costs were
classified as variable costs since they depend on the throughput of the plant. In times of low demand of hydrogen,
the variable costs will be lower and vice versa. In this analysis, it was assumed the plant runs at 100 % capacity for
8000 hrs/yr. As an example, a typical compressor was costed on an annual basis, given in Appendix C-2. In the
interest of keeping this report concise, only the overall variable costs will be provided. The sum of all of these
individual plant equipment operating costs in /yr make up the total operating costs of the plant. The total variable
cost is the sum of the total operating costs and the natural gas annualised cost. Table 9-2 highlights the difference in
operating costs of the two proposed designs. The value and discussion of the natural gas annualised cost will be
explain further on.
Table 9-2: Calculated annual operating cost for each design
Variable
Annual Operating Cost (M/year)
Annual Variable Costs (/year)
Design 1 (SMR with MEA CC)

11.8
37.7
Design 2 (Membrane SMR with CLC)

7.44
26.1
9.4 Estimating the Hydrogen and CO2 revenues, and Natural Gas Annualised Cost
The feed and product flowrates of natural gas, hydrogen and CO2 respectively have been calculated and are
presented in the Table C-2-2 and Table C-3-1 in Appendices C-2 and C-3. In order to calculate the revenues generated
from selling the hydrogen and CO2, a selling price of hydrogen and CO2 must be established. There are a few ways to
approach this problem. One is to consider who the main buyer of the hydrogen is, and agree a price with them. Since
all of the product hydrogen is being sold to chemical companies based in the UK, as stated in the remit, this is how
the price should be established in practice; however, since the chemical companies are not realised, a firm price
would be difficult. Therefore, the other method is to research typical hydrogen selling prices from SMR plants,
compressed liquid CO2 selling prices, and current natural gas prices, in order to get annualised revenues and costs for
product and feedstock. This was the method adopted for both of these designs.
45
GROUP 1

Volume 1
The problem with this method is that reliable cost data is difficult to procure partly because companies are
unwilling to divulge their selling prices, and partly because the prices (especially of hydrogen) have fluctuated quite
wildly in the past few years. A result of this is that taking one single figure as a price for a commodity is likely to be a
highly inaccurate figure for the 20 year period starting in 2018. This problem was partially remedied by constructing
a range of possible prices of each commodity based on data found within the past 20 or so years, and giving an
indication of what the expected price would be in the next 20 years based on recent market trends and expert
opinion.
9.4.1 Hydrogen Revenues and their Uncertainty
It proved difficult to retrieve reliable hydrogen pricing data. One source from the [105] quoted hydrogen prices in a
range from $0.18 to $0.80 per 100 standard cubic feet back in 2003. Once converted to 2018s GBP and to metric
units, this works out to be between 715 and 3170 per tonne of hydrogen. This range is clearly far too wide to be
useful by itself, so additional sources were sought. Two more [106] [107] both quoted hydrogen prices to be around
$3 per kg. Converted to 2018 prices, this equates to around 2250 per tonne of hydrogen. Since this lies between
the boundary estimates given by the ICIS, 2250 per tonne of hydrogen was taken as the median (middle) value for
the hydrogen selling price. In general, it would seem that the price of hydrogen in the future looks promising. With
increasing interest in fuel cells, combined with improving agricultural practices in developing countries leading to
greater demand of ammonia for fertilizer, and in turn, hydrogen, it is not unreasonable to believe the price of
hydrogen could rise in the future. Thus, the mode price of hydrogen (most common, or most likely) was estimated to
be higher than the median at around 2600/tonne. These assumptions about the hydrogen price have a very large
impact on the profitability of the process, so all conclusions drawn should be taken with caution.
Finally, to give an insight into the likelihood of one hydrogen price occurring during the 20 year life of the plant over
another price, uncertainties in the form of p-values were assigned to the prices. Due to the suggestion that future
prices look favourable for hydrogen, the natural distribution of price was skewed negatively, which means higher
prices are more likely to occur than lower prices. For example, the lowest price in the range from ICIS dated in 2003,
715 per tonne of hydrogen, was disregarded under the reasoning that over the 20 year period of the project, the
price is highly unlikely to ever drop that low. Likewise, the median value of 2250 was assigned P50 to state that
there is a 50% probability of the price being either above or below this value. Based on the research done on the
health of the hydrogen economy, it is believed that the mode price will be above this, at an estimated price of 2600
per tonne. Finally, the upper limit of the hydrogen price in 2003, 3170 per tonne, was assigned P10 and therefore it
was assumed only 10% of the time the price will fluctuate above this point. A summary of the commodity prices,
including hydrogen, are provided in Table 9-3.
Table 9-3: Expected prices for the products and feedstock
Commodity
Hydrogen
CO2
Natural Gas
Expected Price (/tonne)

2360
9.72
160
9.4.2 CO2 Revenues

The price of selling CO2 was estimated in a very similar manner to that of hydrogen. However, after performing some
CO2 market analysis, it became clear that supply of CO2 is outstripping demand; therefore it is generally agreed that
future CO2 prices will be similar or lower than they are today [108], around 4.03 - 15.40 per tonne of CO2 in 2018
money. Thus, 4 per tonne was taken as the P99 value, 9.72 per tonne the P50 value, and 15.40 per tonne the P10
value; this time, since future prices of CO2 look bleak, the mode price of CO2 was shifted to below the median price
at around 8.00 per tonne. In general, because the value of CO2 is much lower than that of hydrogen, the revenue
generated from selling by-product CO2 was much lower at all price ranges than the revenue generated from selling
hydrogen.
9.4.3 Natural Gas Costs
It was assumed the price of natural gas will remain relatively constant for the next 20 years at around 160 per
tonne [9]. Table 9-4 summarises the Hydrogen and CO2 revenues along with the expected Natural gas cost per year.
46
GROUP 1

Table 9-4: Revenues and Feed Costs
Expected Value Case

Hydrogen Revenue (M/year)
CO2 Revenue (M/year)
Natural Gas Cost (M/year)
Design 1
98.6
4.00
25.9
Volume 1
Design 2
98.6
2.90
18.7
9.5 Estimating the Total Cost of Production

The total cost of production takes into account the equipment operating costs and feed natural gas costs as variable
costs, along with many other annual costs typical plants have. These include direct production costs (operating
labour, supervision, maintenance, supply, laboratories and patents), fixed manufacturing (depreciation and taxes
and insurance), overheads and general expenses such as administration, distribution and selling, and research and
development. All of these can be estimated empirically. The methodology chosen is in Appendix C-2. Calculated
results are in table 9-5.
Table 9-5: Total Cost of Production of both Designs
Variable
Total Cost of Production (M/year)
Design 1
63.9
Design 2
44.8
9.6 Estimating the Annual Net Profit

The net profit was calculated using the following formula with reference to Appendix C-4:
=
Eq. 33
Table 9-6 displays the net profit of the mode price range for both designs.
Table 9-6: Annual Net Profit of both designs

Mode Case
Net Profit (M/year)
Design 1
38.7
Design 2
56.8
9.7 Calculating the Annual Depreciation of the Plant

Since the lifetime of the project has been designated as 20 years, using a linear depreciation model is not going to be
an accurate prediction of how the inherent value of the plant decreases over time due to wear-out of machinery etc.
Instead, a declining balance model provides a more realistic estimate. Detailed calculations for plant depreciation is
displayed in Appendix C-5.
9.8 Discounted Cumulative Cash Flow, NPV and Uncertainity of the Two Designs
Appendix C-6 contains the relevant calculations for DCFRoR, NPV and Profitability index while Figures 9-1 and 9-2
displays the Discounted Cumulative Cash Flow over the 20 year working life of the plant. The Net Present Value
(NPV) is the final cash flow at the end of the 20 year period. It is clear the general trend is for design 2 (Membrane
SMR with chemical looping) to be more profitable than design 1. Design 2 has a lower capital cost due to having less
equipment and a smaller plant; it also has a significantly lower operating cost. This can be explained by the fact
Design 2 requires the purchase of less natural gas for both feed and heating duties than design 1, due to more
efficient recycling of heat; design 2 also has lower compression costs and catalyst disposal costs. The result of this
means Design 2 has a much greater profit margin which results in an overall higher NPV of the project.
Regarding the economic risks of the two projects, it would appear that Design 2 is less risky. The P90 hydrogen price
(where P90 values are generally considered to be the worst case for long term economic investment into projects)
still results in an overall NPV of 110 million for design 2 compared to design 1, where the break-even point is almost
reached after 20 years. However, it cannot be stressed enough that this economic analysis is very preliminary. It is
suggested this be treated as a class 4 estimate with an accuracy of +/- 30 %. It has been shown that the predicted
price of hydrogen has a huge influence on the profitability of the plant, as does the price of natural gas feed, which
47
GROUP 1

Volume 1
has been assumed constant for simplicity. Not only that, the discount factor (a function of the cost of capital and the
interest rate) can only be empirically determined; a 10 % interest rate was used in this analysis, with a 2% inflation
rate adjusting it to 8%; but in reality, it is likely Costain might see lower interest rates from their investor since
Costain is a well-established and reputable company.
Figure 9-1: Discounted Cumulative Cash Flow for Design 1 (SMR with MEA)
500
P10, 3170/te H2
Millions of
400
Mode, 2600/te H2
Expected Value, 2360/te
H2
300
200
100
0
0
10
-100
12
14
16
18
20
Year
Figure 9-2: Discounted Cumulative Cash Flow for Design 2 (CLC with Membrane SMR)
500
P10, 3170/te H2
400
Mode, 2600/te H2
Expected Value, 2360/te
H2
Millions of
300
200
100
0
0
-100
10
12
14
16
18
20
Year
Table 9-7: Expected price of H2
Economic indicators
Design 1
Design 2
Fixed Capital (M)
87.0
56.4
Cost of Production (M/year)
63.9
44.8
NPV (M)
141
265
Payback Period (y)
5.5
3.5
DCFRoR
0.25
0.41
Profit to Investment Ratio
1.62
4.69
Details on how each of the parameters were calculated in Table 9-7 are given in Appendix C-6.
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10 Start up and Shut down

Design 1 Start-up: An inspection is required to confirm all maintenance work has been correctly completed and
finished, and that all valves and auxiliary equipment are in the correct position. A tightness test of burner block
valves on the furnace is carried out to avoid leakage of fuel into the fired space before start-up. All process
equipment are then purged with nitrogen, all flow introduced at this point is vented to an appropriate flare system.
A leak test is performed, pressure drop should not be more than 0.1 bar per hour. All cooling water streams for
coolers in each section must be turned on prior to the section start-up, the same applies to steam supply for heaters.
To begin start-up, the MEA carbon capture unit is brought online to ensure it is ready to receive and treat the flue
gas from furnace. The knock-out drums V-401 and V-402 should be filled to the normal operating level with water.
Surge drum V-403 filled to the normal operating level with 30 wt% MEA solution. Next the reboiler is filled with 30
wt% MEA solution. Steam should be introduced to the reboiler slowly at first to avoid thermal shock. The stripping
column should be operated in full reflux to get the stripper up to the required temperature of around 100 C. The
pumps P-402, P-403 and P-404 should be primed with a 30 wt% MEA solution to avoid the pumps dead-heading and
causing damage to the impellers. At this point, the lean amine should be pumped into the absorber and the rich
amine pumped into the stripper. This completes the circulatory loop. Next the compressors P-401 and P-501 to P503 should be switched. Now the MEA Carbon Capture Unit is ready to receive flue gas.
A sample feed stream, pre-heated to 30 C via E-101 and pressure checked to 33 bar(a), is introduced to the
desulphurisation unit. Compressor P-101 acts as a backup to ensure that the inlet gas pressure is at the required
specification. Stream U1 is an optional water injection stream which acts to water saturate the feed gas before
entering the columns but variants of the suggested Sulfatreat series such as Sulfatreat HP do not require water
saturated streams prior to use (Hawk Energy, 2016). The sample gas is passed through the column and a sample is
taken at the exit stream to ensure that the H2S concentration is <0.1 ppm. Instantaneous steady operating conditions
should be attainable with Sulfatreat desulphurisation because it is an adsorption based process. A higher inlet
flowrate is introduced as it is the only source of fuel for the furnace at start-up, it will then gradually decrease once
the PSA flue gas is available to serve as the main source of fuel.
The pre-reformer reactor is slowly pressurised to the operating pressure at 32.9 bar(a) and heated to 400oC with
nitrogen using E-206. Desulphurised feed is slowly introduced to begin cracking. Heater E-206 is only used at startup, once the flue gas from furnace is available for pre-heating purposes it will be shut off. In the meantime, the main
reformer tubes are slowly pressurised with nitrogen to the operating pressure of 30 bar(a). Nitrogen flows in and out
of the tubes at a flowrate of 30 to 60 m3/h, any flowrate above this range would crush the catalyst and fluidise the
bed.
The furnace should be tested to ensure there is not an explosive atmosphere inside the furnace before ignition of
the burners is attempted. All burners should be lit before the valves to the burners are turned on and a check should
be made on the flame itself instead of relying on indicators shown in the control room. The flue gas fan is started
and adjusted to an appropriate speed to ensure no buildup of gas inside the furnace. The main control valves in the
fuel gas line are opened and fuel gas is then fed to the burner shut-off valves. Flue gas pressure control is set to
approximately -0.3 mbar to facilitate the flow of flue gas while the shut-off valves are opened to allow combustion.
For the purpose of this design, the flue gas temperature should reach 514oC, the furnace is heated by the flue gas at
a rate of 50oC/hour until the desired temperature which would take around 10.5 hours.
While the furnace is heating up at a steady rate, steam is introduced into the reformer tubes while proportionally
reducing the flow of nitrogen, with the flow through each tube high enough to avoid overheating the catalyst. The
temperature at the outlet of the tubes needs to be recorded to confirm that the heating rate is within the limits.
When the temperature of the reformer tubes is satisfactory and no additional nitrogen enters the tubes, feed from
the pre-reformer outlet is introduced slowly at first and gradually increased in order to ensure temperature remains
constant. As long as the composition control at the tubes outlet indicates a satisfactory outlet composition the flow
can be directed to the next downstream unit the Water Gas Shift (WGS) Reactors. The temperature control loop is
first turned on for cooler E-201. Both reactors are then pressurised with nitrogen to an operating pressure of 30 bar
for the HTWGS and 29 bar for the LTWGS. The product flow from SMR is introduced between the first and second
WGS. The temperature control loop is turned on for E-202 and E-203. A composition test after the WGS indicates
whether the flow is of suitable quality for the Pressure Swing Adsorption (PSA) unit, situated downstream. If the
composition is unacceptable the flow is sent to the flare until correct composition is achieved.
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The PSA unit will be pressurised at the same time when feed is first introduced into the reformer tubes, it is
recommended to pressurise the beds with H2 gas rather than N2 to preserve the adsorbents. This results in an
additional reserve feedstock of H2 to be purchased, stored and used during start-up. The columns will undergo full
cycle schedules until cyclic steady state is reached. This is estimated to be 25 minutes or longer to allow every
column to go through every stage at least once. Once cyclic steady states are recorded in the columns, qualified
outlet from WGS can then be introduced to purify hydrogen and sent to storage. PSA flue gas is sent to furnace as
the main source of fuel, at this point the desulphurised natural gas feed to furnace can gradually decrease.
Normal Operation: Under normal operation, natural gas feed sweetening by the desulphurisation unit simply
involves having the feed pass through a single column (T-101 A or B) with no additional special requirements.
Composition control indicators are located at different points throughout the bed to monitor the H2S buildup stain
front (Maddox, et al., 1982 p. 219) through the bed. Once the stain front reaches a predetermined level, which is
usually near the estimated breakthrough time of the bed (1 year based on our design), any feed gas currently going
through the spent bed will be redirected to the second (standby) bed. The new feed gas will also be redirected to the
standby bed and operation will continue as normal. The spent column will be nitrogen purged before being dumped
and fresh adsorbent is added. Spent Sulfatreat does not coagulate or stick to the column walls so adsorbent
changing should only take a day without a required shutdown. A final sample point is located at the end stream
(stream 3) of the column to allow additional composition checks and act as a backup in case the composition
indicators are failing.
The furnace has a total duty of 119 MW, in which 47.5 MW is required by the endothermic Steam Methane
Reformer (SMR) reaction, while the remaining energy is used for pre-heating purposes of the pre-reformer inlet and
steam methane reformer inlet. Under normal operation, a ratio of 1.1 excess air to fuel is used to guarantee
complete combustion. If there is a sudden change in the fuel gas composition, adjustment to the air blower is made
accordingly. There is also a sample point located at the flue gas exit (stream 15) to check for oxygen and carbon
monoxide composition, this acts as a backup in case the composition indicator upstream of the furnace fails.
Temperature is measured by pyrometers at various points in the furnace. A local exceptionally high temperature
might indicate a coke formation within the furnace. If the temperature exceeds 1200 oC, the furnace must be shut
down to prevent the reformer tubes from melting.
Product stream (stream 8) from SMR is cooled to 402oC by E-201 for High Temperature WGS reactor to convert
carbon monoxide into carbon dioxide, it is then further cooled down by E-202 and E-203 to 240oC for Low
Temperature WGS reactor to further increase the conversion of hydrogen and carbon dioxide. WGSs are slightly
exothermic reactions; therefore it is important to monitor the temperature within the reactor. If the temperature is
too high (15% higher than normal operation) a high level alarm would go off and a trip system would set off allowing
water to circulate in the cooling jacket of the reactor.
Followed by PSA unit, normal operation for a single column (Eg: T-301) starts with the feed gas mixture of CH4, CO2,
N2 and CO (Stream 11) simply owing through the column at the designed temperature and pressure of 30 C and 25
[bara]. This stage is called the feed step whereby every other species and a small fraction of H2 is adsorbed onto the
activated carbon/zeolite adsorbent bed. The non-adsorbed H2 gas leaves the column at 99.99%+ purity in most cases
via stream 12 but composition indicators are installed to guarantee product specification.
The feed step lasts up until before the breakthrough point of the adsorbent bed (~4.2 minutes) after which the exit
valve is shut and the pressure equalization valve to column T-305 is opened. This step is called pressure equalization
1. This step is repeated 3 times following the suggested cycle schedule (Table 6-5) first with column T-304 and finally
with column T-303. It is worth noting that 3 pressure equalization steps are used in this cycle schedule to ensure a
higher recovery (>90%) of H2 per cycle. The next step is the purge preparation (providing purge) step whereby the
purge valve to column T-302 is opened. Note that T-302 will undergo purge at this stage of the process. Purge
preparation is similar to the pressure equalization stage but the receiving column will be purging its gas rather than
pressure equalizing.
After purge preparation, column T-301 will undergo blowdown whereby the gas left is sent to stream 13 as PSA offgas. Again, purge involves the same principle but this time column T-306 which is undergoing the purge preparation
step feeds the remainder of the unrecovered product gas (H2) through column T-301 which desorbs the other
species (CO2, etc.). This mixture once again leaves the PSA section via stream 13 as PSA off-gas. After this stage,
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column T-301 is now on the receiving end of the pressure equalization step from columns T-305, T-304 and T-303
with 2 idle steps in-between. Idle steps are times when the column is not doing anything.
Finally, column T-301 will undergo re-pressurization by product. Although re-pressurizing by product rather than
feed seems counter-intuitive, this method is generally preferable as product purity is higher since the adsorbent
wont be used before the actual feed is introduced. This cycle schedule consists of 11 steps total with 2 idle steps inbetween. Every column follows the same schedule according to Table 6-5 with a designated overall cycle time of 2025 minutes.
Under normal operation the MEA absorption column (T-401) should be operating at 40 C and 2.8 bar(a), and the
stripping column (T-402) should operate at 120 C and at atmospheric pressure. There are composition indicators to
monitor the flue gas inlet compositions into the absorber to make sure there is no unusually large CO2 flow rate
entering the column. The ratio of CO2 in the stack gas to CO2 in the inlet gas (stream 18) is controlled by manipulation
of the amount of lean amine solution entering the column. For the stripping column the rich amine stream (Stream
19a) enters from the second tray from the top of the column at 70 C. There are no special requirements for the
stripping column, only major concern will be to monitor the temperature of the reboiler via the temperature indictor
controller.
Shutdown: For plant (planned) shutdown, the natural gas feed is turned off for desulphurisation columns, inlet flow
to the pre-reformer and SMR decrease gradually, the reduced product flowrate from the SMR will flow through both
WGSs and go to the PSA. When the flow stops, each process equipment unit is isolated from any up- or down-stream
units and the vessels are purged with nitrogen to the flare.
While for the furnace, firing should be continued but at a significant reducing rate of 50 oC/hour after feed flow into
the reformer is stopped. This is done to ensure a controlled steady decrease of temperature and pressure inside the
reformer tubes. Some burners would have to be isolated by closing some of the shut-off valves, the sequence of
burner isolation should be done in a way to provide a uniform reduction of temperature in the furnace. The main
control valve in the fuel gas line should be closed when a low flue gas temperature is reached. After the fuel gas is
isolated, the remaining burner shut-off valves can also be closed. The cooldown rate is controlled by adjusting the air
flow.
After the flue gas flow from the furnace has stopped, all pumps and compressors should be switched off as well as
the steam flow to the reboiler. Shut-off valves on the CO2 compression line should be closed to prevent accidental
production of below-spec product CO2. This will halt CO2 production and the whole plant will be come to a standstill.
Unusual Features: The unusual feature of start-up and shutdown for Design 1 is that the steam methane reformer
tubes are situated inside the furnace radiant section. Both pieces of equipment are heated up and cooled down at
the same rate of 50oC/hour, but the reformer tubes would reach the desire temperature slower than the furnace as
it takes time for heat transfer by radiation to occur, extra time should therefore be allowed for reformer tubes to
reach a steady state. It is extremely important to monitor temperatures at different points inside the furnace
especially during start-up to make sure they are not near the melting point of reformer tubes.
Steady State Time Span and Start-up Sequence:
The first section to undergo start-up is the MEA apparatus, this takes 8.5 hours. The next section is the carbon
compression chain which take 2 hours, this finishes start-up at the same time as MEA. After these 2 sections
complete their start-up the furnace and the SMR section begin start-up at the same time, these take 10.5 hours and
13.5 hours. The next stage to begin start up is the desulphurization bed, which takes 0.5 hours. This leads into the
start-up of the pre-reformer, which takes 6.5 hours. After this the PSA stage begins start up and takes 0.5 hours to
complete. After all of these stages have reached steady state the water gas shift start-up begins, this takes 3.5 hours.
The total time required for start-up is estimated to be ~22 hours with reference to Table H-1 in Appendix H: Start-up
times.
Difference between Normal Shut-down and Emergency Shut-down:
In the case of one or more of the flames in furnace goes out, fuel may leak through the idle burners and form a
flammable mixture inside the furnace, which can be ignited by other operating burners. An explosion may occur in
the worst case scenario. Another case would be when the furnace temperature is close to the melting point of
reformer tubes which is at 1200oC, an emergency shut-down is required. The main difference between normal shut51
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down and emergency shut-down is that all inlets are gradually decreased in the former one, while all inlets are shutoff immediately in the latter one. Air flow is adjusted to cool down the furnace at a higher rate than a planned shutdown. After the reasons for initiating an emergency shut-down are identified and resolved, proper start-up
procedure should then be followed.
Design 2: Start-up: All pipework and vessels are initially purged with nitrogen to remove debris, for heating purposes
and to pressurise if necessary. Reactors R-202 and R-203 must be pressurised to 25 bar(a), pre-reformer R-201 must
be pressurised to 33 bar(a), vessels V-202, V-201 and V-302 must be pressurised to 25 bar(a). Meanwhile vessel V301 must be pressurised to 2 bar(a) and the desulphurization columns T-101 A/B presssurised to 33 bar(a). All
cooling water streams for coolers E-207, E-206, E-204, E-205 and E-301 must be turned on. Steam for heaters E-101,
E-201, E-202 and E-203 must also be turned on. Utility streams U1, U3, U4 and U10 must be online. SMR Membrane
tubes must be gradually filled with nitrogen until the optimal reaction temperature is acquired. Stand-by
compressor P-101 and CO2 compressor P-301 must be brought online. Pump P-204 should be primed and ready to
transport the product CO2.
Catalysts must be inserted where needed. This includes Sulfatreat in columns T-101A/B, Nickel Oxide in prereformer R-201 and Nickel particles in air reactor R-203. Appropriate PPE must be worn and extra care taken when
handling these substances.
To begin process start-up, the desulphurisation unit is brought online, this follows the same procedure as design 1.
Introduce the natural gas feed to the pre-reformer slowly to begin cracking.
As the temperature produced from the chemical looping system is stabilized by the endothermic reaction in the SMR
Membrane tubes, to avoid a runaway reaction the entire CLC SMR Membrane system must be initiated
simultaneously. The Air Reactor feed (stream U9) is introduced to begin fluidization. The Fuel Reactor feed (stream
14a) is slowly introduced to begin combustion and heat generation, with 15% of stream 3 being directed to the Fuel
Reactor at the same time as fuel is introduced to the SMR Membrane tubes from the pre-reformer for subsequent
reaction. The off gas product from the SMR Membrane reaction is then combined with stream U6 for recycle into
the Fuel Reactor.
A composition indicator on the fuel reactor product stream (15) indicates the effectiveness of combustion. The
product stream is sent to the flare until the required specification is met. A split range control system dictates the
flowrates and hence ratio of fuel:air entering both reactors. Once complete combustion is achieved (noted by the
presence of only water and carbon dioxide by the gas analyser) the product stream is sent to cooler E-205 to for
subsequent separation and compression of carbon dioxide.
The SMR Membrane tubes are fed slowly with fuel initially for controlled combustion. The product stream is then
sent to cooler E-205 for subsequent separation.
Normal Operation: Under normal operation the natural gas feed is stripped of its sulphur content, and split between
the pre-reformer and the fuel reactor. The CLC reactions generate the heat required to produce hydrogen, and the
carbon dioxide is captured and compressed. Utility streams functioning as make-up steam (U3, U4, U7, U10) must be
monitored closely for the process to run at optimum conditions.
The CLC reactors operate in harsh environments. As fluidized beds, they require close supervision and monitoring to
ensure critical maintenance and repair is anticipated.
Particle attrition is a serious problem in fluidization processes, with many contributing factors. These include
continuous high velocity impact on cyclone walls and continuous low velocity impact from bubble abrasion.
Unfortunately particle attrition cannot be avoided, and so close monitoring is required to periodically replace the
particles for efficient operation. As particle attrition rates are very specific to each operating environment and
conditions, a record can be complied over the operating life of the system to identify more accurate time frames in
which the particle degrades.
Particle sintering is another potential problem caused by high temperatures. Sintering occurs when surface
molecules rearrange themselves to match and form larger particles of reduced surface area. Again, careful
monitoring is advisable.
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As the oxygen carrier is transported to the top of the fuel reactor via the cyclone and falls parallel to the vertical SMR
tubes via gravity, the particle force on the outside of the tubes must be considered. Regular inspection of the tubes
must be scheduled to maintain their mechanical integrity.
The cyclone in design has been modeled as a reverse flow cyclone, assuming complete separation efficiency
between the particles flowing downwards and the gas flowing downwards. However in practice complete
separation may be unachievable, leading to potential particle entrapment. To prevent cyclone fouling, regular
cleaning must be undertaken.
Each equipment piece should be regularly inspected externally, under normal operation, for evidence of rust and
corrosion.
Shut-down: Concurrent and controlled shut down of the CLC SMR Membrane system is extremely important to
avoid the risk of excess heat destroying the membrane tubes. The feed to the SMR Membrane tubes should first be
stopped with the reaction coming to an end and nitrogen should be inserted instead to avoid catalyst overheating.
At the same time, the fuel reactor feed should be decreased slowly to control the temperature drop in the reactor
(avoiding thermal stresses). The Air Reactor feed stream (U7) can then be shut off last.
Stream 15 should be sent to flare to prevent partially combusted fuel entering the separator. This prevents impure
CO2 product being compressed, an unnecessary expense and potentially hazardous.
Temperature indicators on the reactors will illustrate when the SMR reaction is unfeasible. At this point SMR feed
should be shut off. The feed stream to the desulphurisation unit should be stopped for complete process shut down.
Utility streams can then be set offline, and the entire system purged to flare to make safe for maintenance.
Unusual Features: Chemical Looping Combustion with SMR membrane technology is an innovative process and
hence extra monitoring and inspection should be given during start-up and shut-down. The most noteworthy feature
of the design is the insertion of the SMR membrane tubes inside fuel reactor, R-202. As a result, introduction of fuel
(stream 14a), air (stream U7) and reformed natural gas (stream 7) must be simultaneous and controlled. This
prevents the generation of excess heat, which in turn avoids reactor meltdown.
The transfer of heat using fluidised bed reactors is a highly sensitive process with a number of factors potentially
contributing to failure. Numerous studies have been completed into the performance of fluidised bed reactors at
extreme temperatures and pressures for chemical looing combustion, however industrial size implementation is yet
to materialise. Particle attrition rates, sintering and agglomeration onto reactor walls will be individual to this
specific case and should therefore be investigated periodically.
If the feed gas was to enter at below expected pressures, compressor P-101 can be brought online to re-pressurise
the stream for the desulphurisation unit.
Steady State Time Span and Start-up Sequence:
The first stage to begin start up is the SMR stage which take 10 hours to reach steady state and spans the duration of
the design 2 start-up timeline. After this the pre-reformer begins its start-up sequence, which takes 6.5 hours,
followed by the air reactor and the desulfurization apparatus, these both take 0.5 hours. All three of these pieces of
equipment reach steady state at the same time. At the point where these three stages reach steady state the startup sequence for the fuel reactor begins, this takes 1 hour to reach steady state. The total time required for start-up
is estimated to be ~10.5 hours with reference to Table H-2 in Appendix H: Start-up times.
Difference between Normal Shut-down and Emergency Shut-down:
In the case of reactor failure (i.e. temperature spike) the process is completely shut-down to prevent irreversible
damage to the expensive SMR Membrane tubes. The process feed stream is stopped immediately, along with the air
reactor inlet stream. This prevents further reaction and heat generation. Once the root cause of the emergency
shut-down has been identified and rectified, the process can recommence, starting with a plant wide nitrogen purge.
Normal shut-down is carried out slowly and methodically to ensure minimum product wastage and maximum
control. This helps avoid thermal shocks in equipment materials, increasing process equipment lifespan.
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11 Recommendations and Conclusions

The overall goal of this section in the report is to review both designs from a technical point of view; providing input
where possible as to the inherent uncertainties and capabilities of both designs. In addition, general process
alternatives and possible improvements will be recommended so that detailed design of the plant can start without
delay. To summarise, a typical hydrogen production plant with integrated carbon capture is made up of 4 critical
parts and for each of these parts, Process Selection was carried out to identify potential candidates with the final
designs shown in Figure 11-1. For reasons mentioned in Process Selection, process alternatives such as Amine
absorption for desulphurisation; Catalytic partial oxidation and auto-thermal reforming for hydrogen production;
Pressure swing adsorption, Sorption enhanced reaction and Cryogenic CO2 capture for carbon capture were not
chosen but still remain very viable looking toward the future.
Design 1
Design 2
Figure 11-1: Proposed designs

Each of the designs presented in Figure 11-1 were evaluated from a technical, safety, economic and environmental
point of view with an overall summary table presented in Table 11-1.
Table 11-1: Summary table for both designs
Comparison Parameter
H2 Recovery %
CO2 Recovery %
Design 1 SMR with MEA

Design 2 CLC with Membranes
89.6
98.8
95
99.99
1. Operates at higher temperatures
Health and Safety Aspect
2. Contains MEA
1. Inherently safer
3. More process equipment in general
1. 5% CO2 release
1. More spent catalyst in the overall
Environmental Impact
2. 0.09 [mg m-3] MEA concentration in
design
flue gas
2. More process water required
NPV after 20 Years (M)
141
265
Maturity of Technology
1. Well established
1. Relatively new
Involved
2. Current industry standard
To conclude, Design 2 is an outstanding candidate that will achieve all the objectives required by the remit in
addition to being very economical, safe and environmentally friendly. However, the rather limited pilot plant and
scale-up data for the processes involved in Design 2 means that the outlook is optimistic at best. Investors should
take heed of this and invest in a pilot plant version of Design 2. If the results are comparable, a full scale plant
investment should be made which would certainly prove very economical in the long run. However, should the
priority shift toward making profits within a reasonable time-span, Design 1 is an excellent candidate as it uses well
established, reliable industry standards with minimal impact on the environment.
11.1 Design Uncertainties and their Importance
Since this report presents just a preliminary design of two different hydrogen production plants, there are inevitably
areas of uncertainty associated with them. These uncertainties are discussed in order of decreasing importance of
their supposed impact on the final designs.
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One of the single largest sources of uncertainty applicable to both designs is the ever-changing prices of hydrogen
and natural gas. In the past ten years, the price of both hydrogen and natural gas have fluctuated wildly. The general
trends appear favourable for Costain to invest in both of the projects, but it is likely that profits could fluctuate yearon-year depending on the state of the prices in that year. Of course this has a large impact on the feasibility of the
designs. It is entirely possible that just by unfortunate chance, natural gas prices sky-rocket and hydrogen prices drop
in the first year of production, and subsequently the plant will see a net lost at the end of that year. Should this
continue for another year or two, then the whole project may have to fold. This is a very unlikely scenario but the
likelihood of it happening should not be ruled out completely.
Many of the large items in the process were designed using simplified models or short-cut methods. Specifically, the
desulphurisation unit and the PSA system were both designed using empirical correlations and short-cut methods
employing rules of thumb. In Design 2, the reactors in the Chemical Looping Combustion System were modelled as
ideal due to the complexity of fluidised bed reactors. The fuel reactor was modelled as a PFR, while the air reactor
was modelled as four CSTRs in series. Furthermore, mass transfer was neglected in both reactor designs. These
assumptions impacted the gas molar flowrates, conversion of the reactant gas and ultimately the volume of the
reactors. In particular, the overall heat transfer coefficient in the SMR reactor for both designs had a significant
impact on the size of the reactor, and thus, the costs. It is difficult to obtain a more accurate prediction of U without
physically modelling the system in real life and conducting experiments to determine it.
An uncertainty for design 1 surrounds the permissible emission limits of MEA to the environment. Currently, the
stack emits 2 ppm (vol). Regulations surrounding MEA emissions based in the UK are not available; however the
USA-based Occupational Safety and Health Administration (OSHA) states the Permissible Exposure Limit (PEL) over
an 8-hour time weighted average (TWA) as 3 ppm (vol). However, this is just one source and few can be found. While
the design is under this limit at steady state, there is not much room for error due to increasing emissions caused by
unplanned events or poor operation.
A last uncertainty worth mentioning is the assumption of no NOx formations in the furnace or fuel reactor. The
uncertainty lies with the temperature range at which thermal and fuel NOxs form. This simplification allows the flue
gases to enter the MEA Carbon Capture Unit without the need for a NOx scrubber on the flue gas line, significantly
lowering capital costs of the MEA process.
11.2 Flexibility of the Proposed Design
In the situation where the demand for hydrogen suddenly increases, ergo Costain decides to increase the capacity of
the hydrogen plant, then the throughput of the plant would have to increase. However, in the case of design 1, the
flowsheet rating of 5 tonnes/hour can only be raised by 6 %, to 5.3 tonnes/hour, without changing any of the
existing units. The limiting factor here is the PSA unit. Above a throughput of 5.3 tonnes/hour H2, the designed PSA
cycle schedule may have to be redesigned; resulting in shorter feed step times. Overall, this does not impact the
production of H2 for the plant but it does reduce the lifespan of the PSA columns as well as forces the PSA section to
run below optimal design conditions.
For the SMR reactors, increasing the flowsheet rating of the plant would require larger reactors. This can be
achieved by inserting more tubes into the reactor vessels. It is believed that the reactors can be scaled up linearly
without any problems.
For the MEA Carbon Capture Unit, if the flowsheet rating of the plant increased by 10 %, to 5.5 tonnes/hour of H2,
10 % more flue gas would be produced. This increase in flue gas flowrate from 6696 kmol/hour to 7366 kmol/h
would cause the absorption capture efficiency to drop to 92.3 % when keeping the solvent flowrate constant. Thus,
during scale up of production, the MEA Carbon Capture Plant would have to be redesigned for a bigger solvent flow
capacity to maintain the 95 % absorption efficiency.
For the feed flow to the process, natural gas is available at 33 bar(a) with 5.1 ppm sulphur. If the natural gas were to
enter at lower pressure, below 30 bar(a), back-up compressor P-101 would switch on and compress the feed to 33
bar(a) for desulphurisation. If Costain were to switch natural gas suppliers to one with a sulphur content above 1200
ppm, then the current Sulfatreat adsorption technique would need to be replaced with a technique which can cope
with high feed gas sulphur content. A secondary technique for desulphurisation was not complete, but a
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recommendation would be a wet-based process using MEA to remove the acid gases, similar to the MEA Carbon
Capture Unit.
11.3 Process Improvements
11.3.1 General
Water knock out vessels separating carbon dioxide and water have been assumed to perfectly separate the two
components. However this will not occur in practice, with the formation of dissolved carbon dioxide (carbonic acids)
creating issues. Henrys Law can be implemented to calculate the dissolved carbon dioxide under pressure and an
alkaline solution could be used to neutralise the stream.
Further information surrounding the catalysts used in the design could help ascertain accurate catalyst lifespans.
This could improve the designs by increasing the time between replacements. Furthermore, exact diameters of
catalyst particles could improve reactivity rates and required volumes for reactors.
The heat exchanger network could benefit from further research to find more accurate Overall Heat Transfer
coefficients (U). This would ensure the surface area of the heat exchangers was accurate. More detailed stream data,
especially surrounding the two phase flow streams, would improve overall heat integration accounting for the flow
regimes associated with vapour-liquid flow. CFD software would facilitate this.
Authentication of all of the kinetic data utilised in designs 1 and 2 would help improve the process, and aid the
reliability of the product flowrates obtained.
11.3.2 Design 1
Introducing a water wash step at the top of the absorption column in the MEA Carbon Capture Unit has the potential
to reduce the residual MEA vapours emitted from the stack down to very low levels. Implementation of this
technology would be a relatively cheap and effective way to solve the MEA emission problem. Upstream of this, in
the flue gas line immediately after the furnace, a scrubber should be installed to capture the NOx before it enters the
system. NOxs are unwanted in a system containing MEA since the NOx speeds up the degradation of MEA into salts
which can clog up the process.
The furnace design needs to be refined as it was significantly overdesigned for the purpose of this plant. This
however allowed us to use the additional heat generated by the furnace for heating purposes throughout Design 1.
Ultimately, the heat generated still exceeds the heat demanded by the plant in design 1, which incurs large thermal
inefficiencies. Removing the assumption of complete combustion would enable the amendment of the furnace and
would reduce this inaccuracy.
Kinetic data for both Water Gas Shift reactors could be verified through laboratory experiments as the data available
was wide ranging and sometimes conflicting.
11.3.3 Design 2
In terms of the short cut methods utilised, more detailed models would aid the improvement of this design and also
help validate the proposed designs. For example, the fuel reactor in Design 2 could be modelled as a counter-current
moving bed reactor increase the accuracy of modelling the bubbling fluidisation regime. The air reactor design in
Design 2 could be enhanced with the use of solid void fractions representing the varying fluidisation regimes. Solid
voidage calculations could not be accurately performed without in depth investigation into the solid voidage at the
outlet of the reactor and decay indexes. Incorporating a solid voidage fraction into the design of the air reactor
would significantly improve its accuracy and performance prediction.
56
GROUP 1

Volume 1
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Carbon monoxide safety data sheet, C. NV, Editor. 2015: Belgium.
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Nickel Alumina Catalyst safety data sheet (PRICAT 9920), J. Matthey, Editor. 2003: OAKBROOK TERRACE, IL
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Nitrogen safety data sheet, B.G. Ltd, Editor. 2015: Worsley, Manchester UK.
Oxygen safety data sheet, B.G. Ltd, Editor. 2015: Worsley, Manchester UK.
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Propane safety data sheet, B.G. Ltd, Editor. 2011: Worsley, Manchester UK.
Sulphur safety data sheet, J.M.L. plc, Editor. 2002: Southampton, Hampshire.
Zinc Oxide safety data sheet, J.M.L. plc, Editor. 2002: Southampton, Hampshire.
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Environment: London.
2011/278/EU: Comission Decision of 27 April 2011 determining transitional Union-wide rules for harmonised
free allocation of emission allowances pursuant to Article 10 a of Directive 2003/87/EC of the European
Parliament and of the Council. 2011, European Parliament: NA.
Higher CO2 price would help EU utilities, but remains a pipe dream, in Carbon Pulse. 2015, Carbon Pulse.
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Washington, DC.
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Anon.
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Santori, G., Pinch analysis notes. 2016, Edinburgh University: Edinburgh.
Martion, A. and F.A. Mato, HINT: An educational software for heat exchanger network design with the pinch
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A. Kohl, R.N., Gas Purification. 1997: Gulf Professional Publishing.
60
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Volume 1
Appendix A: Heat integration

Heat integration for both designs was attempted using basic pinch analysis principles from[109]. Due to the presence
of phase changes in the streams selected for the heat exchanger network, [110]was used together with HINT (Heat
exchanger network software) to determine the heat cascade of the system and allow iterative allocation of the heat
exchangers in the system to complete a minimum energy required network. Property data was taken from the
energy balance table to predict the MCp values used in the pinch analysis. Due to time constraints, approach
temperatures and overall heat coefficients were not optimized although the HEN (heat exchanger network) is
thermodynamically sound. This will mean that certain heat exchangers will either be too large or too small to carry
out their duty. The critical review section will address this in further detail.
Figure A-1: Grand Composite Curve for Design 1
Figure A-2: Proposed Heat Exchange Network using HINT (Design 1)

61
GROUP 1

Volume 1
Table A-1: Heat integration network exchangers for Design 1

Heat
exchanger
Description
E-101
Gas-Gas exchange
E-601
Gas-liquid exchange with phase

change
E-602
Gas-Gas exchange
(Superheated water)
E-603
Gas-Phase change liquid
E-604
Gas-Liquid exchange (up to

saturation point)
E-605
Gas-Liquid exchange with phase

change and superheating
E-505
Gas-Cooling water exchange
E-402
Liquid-Cooling water exchange

with phase change
E-401

with phase change
E-201
E-202
Heat transfer
coefficients
[kW m-2 K-1]
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 2
Cold: 2
Overall: 1
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 2
Cold: 2
Overall: 1
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
TLMTD
[K]
91.4
Estimated
duty
[MW]
0.23
Estimated heat
transfer area
[m2]
12.6
10.4
7.74
744
152
3.98
131
526
20.0
126
255
7.47
97
656
4.13
21.0
50
1.02
70.0
50
73.8
1476
50
105
7000
50
7.08
472
50
2.24
149
62
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Volume 1
Figure A-3: Proposed Heat Exchanger Network Design 1
Figure A-4: Grand Composite Curve for Design 2
63
GROUP 1

Volume 1
Figure A-5: Proposed Heat Exchanger Network using HINT Design 2

Heat
exchanger
(Above pinch)
E-203
Description
Gas-Gas exchange
E-202
Gas-Gas exchange
E-607
Gas-Gas exchange
E-610
Gas-Gas exchange
E-605

change
E-207

change
E-611

change
E-608
Gas-Gas exchange
Heat transfer
coefficients
[kW m-2 K-1]
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 0.4
Overall: 0.2
TLMTD
[K]
4.45
Estimated
duty
[MW]
0.97
Estimated heat
transfer area
[m2]
1090
13.6
0.20
73.5
69.4
2.35
169
14.3
13.3
4650
55
2.307
140
302
0.946
10.4
38.8
7.17
615
21.4
3.77
880
64
GROUP 1
E-612
E-606
E-609

Liquid (phase change)-Heating Hot: 2
50
gas/liquid exchange
Cold: 2
Overall: 1
Liquid(phase-change)-Heating Hot: 2
50
gas/liquid exchange
Cold: 2
Overall: 1
Gas-Heating gas/liquid
Hot: 0.4
50
exchange
Cold: 2
Overall: 0.3
Volume 1
6.89
137.8
0.83
16.6
0.63
42
Figure A-6: Proposed Heat Exchanger Network Design 2
65
GROUP 1

Heat
exchanger
(Below pinch)
E-101
Description
Gas-Gas exchange
E-601
Liquid-liquid exchange
E-602
Gas-liquid exchange
E-603
Gas-liquid exchange
E-604
Gas-Gas exchange
E-301
E-204

with phase change
E-208
E-205
Gas,Liquid-Cooling water
exchange with phase change
E-206

with phase change
Heat transfer
coefficients
[kW m-2 K-1]
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 2
Cold: 2
Overall: 1
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 2
Cold: 2
Overall: 1
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 2
Cold: 2
Overall: 1
Hot: 2
Cold: 2
Overall: 1
TLMTD
[K]
Volume 1
95.4
Estimated
duty
[MW]
0.18
Estimated heat
transfer area
[m2]
9.43
0.78
5.64
7230
40.1
1.06
88.1
3.4
0.29
284
21.6
6.77
1567
50
0.75
50
50
11.1
222
50
0.96
64
50
112.8
2256
50
19.4
388
66
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Volume 1
Appendix B: Environmental impact sample

calculations
Sample calculation X: Maximum concentration downstream from stack
Using notes from[111], the equation for elevated continuous point source release is:
(
(, , ) =
B-1
Where c is the concentration in [g m-3], Q is the component release rate [g s-1], u is the wind speed [m s-1], H is the
stack height [m]. y is the concentration variation, z is the vertical coordinate [m] and x is the horizontal distance [m].
Only the maximum ground level concentration needs to be calculated. Therefore, y = 0 for maximum concentration
and z = 0 for ground level conditions. Furthermore, at an elevated source (stack height) of 50 [m] or more:
= = 0.0707
B-2
The overall equation for elevated continuous point source release simplifies to:
(, , ) =
2(0.05
(
( .
( )
.
( .
B-3
Therefore, the maximum concentration at ground level as a function of distance away from the source at a release
rate of 0.49 [kg h-1] or 136111 [g s-1], designed stack height of 80 [m] and a conservative wind speed of 5 [m s-1]
[112]is:
Table B-1:
X [m]
10
50
100
200
300
400
500
1000
C [g m-3]
1.11305E-45 2.032048 72.31581 89.17726 59.55507 40.46985 29.01764 9.393212
C [mg m-3]
1.11305E-48 0.002032 0.072316 0.089177 0.059555
0.04047
0.029018 0.009393
Sample calculation X: Calculation of CO2 allowance per year

Using the discussed allowance of CO2 released per tonne of product[97], the 5 [tonne hr-1] capacity of the plant, an
estimated 8000 [hr yr-1] and the factor applied for 2019 allocation[97], the estimated allocated allowance of CO2 per
year should be:
8.85
5
8000 0.3714 131476

B-4
67
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Volume 1
Appendix C: Economic Analysis calculations

C1: Capital Cost Estimate
When it came to estimating a purchase cost of columns, drums, and tanks, the height and diameter of the vessel
were used to estimate the cost of the equipment in 2004 terms. Figure C-1 refers to vertical vessels; C-2 to
horizontal vessels, and C-3 to the plates of columns [102]. The numbers of the lines 1-4 refer to the diameter, where
1 = 0.5m, 2 = 1.0m, 3 = 2.0m, 4 = 3.0m. Once this point was identified on the graph, the retrieved purchase cost was
multiplied by the relevant pressure factor, and also multiplied by a material factor, and then finally multiplied by the
inflation factor (obtained from the CEPCI index, Figure C-6-1). Both designs generally only used either carbon steel or
stainless steel; the material factor takes this into account, since stainless steel is more expensive than carbon steel.
Sample calculation C-1 shows how this is done.
Figure C-1-1: Costing Vertical Vessels
Figure C-1-2: Costing Horizontal Vessels
Figure C-1-3: Costing Plates in Columns (1 = Sieve plate, 2= valve caps, 3= bubble caps)
68
GROUP 1

Volume 1
Sample Calculation C-1:

Using the CO2 hold-up tank in the CO2 compression train in Design 1 as an example, it is a vertical vessel with a
diameter of 4m and a height of 11m. It is made from carbon steel, so its material factor is 1; however it is at a
pressure of 70 bar(a), so the pressure factor is accordingly 2.5. Thus, the purchase cost of this tank is approximately:
= 18000 1 2.5
= 18000 1 2.5
650
= 66,500
440
C-1-1
C-1-2
The installation cost of the equipment was then calculated by multiplying the purchase cost by the relevant Wroth
factor. For tanks, the Wroth factor is 3.5.
= 66,500 3.5 = 233,000
C-1-3
As for the purchase cost of heat exchangers, pumps and compressors; the method employed was the same for all.
Either the volumetric flowrate (pump), power requirement (compressor) or heat exchange area (HX) were used in
the equation as the parameter S:
= +
C-1-4
Where a, b and n change depending on the application. If the sizing parameter S was above the upper limit described
in the six tenths rule was used to scale up the cost of the item. The six tenths rule can be found from a wide variety
of literature and is thus:
=
C-1-5
Where C1 and S1 are the cost and size of equipment item 1 respectively, and C2 and S2 are the cost and size of
equipment item 2 respectively. N is 0.6 to represent that the cost of items generally dont scale up linearly; hence
being dubbed the six tenths rule.
The sum of the installation cost of every piece of process equipment is the Inside Battery Limits Cost. For brevity, this
is not shown. Table C-1 shows the steps required to calculate the Total Capital Cost.
Table C-1: Total Capital Cost Estimate
Variable
ISBL
OSBL (50 % of the ISBL)
Engineering Costs (20% of ISBL + OSBL)
Contingency (10% of ISBL + OSBL)
Partial Fixed Capital Investment
Location Factor [UK]
Fixed Capital Investment (FCI)
Working Capital (10 % FCI)
Total Capital (FCI + WC)

43.7
21.9
13.1
6.56
85.3
1.02
87.0
8.70
95.7

28.4
14.2
8.51
4.26
55.3
1.02
56.4
5.64
62.1
The annualised fixed capital investment (AFCI) payable to the investor for providing the capital investment is given
by equation (X). A =n I = 5% interest rate was used, payable over the n = 20 year lifetime of the project. For Design 1:
=
(1 + )
(1 + ) 1
C-1-6
69
GROUP 1

0.05 (1 + 0.05)
() = 87.0
= 6.98
(1 + 0.05) 1
Volume 1
C-1-7
For Design 2, under the same loan conditions, the AFCI was found to be 4.53 million.
C2: Total Cost of Production Estimate

The total cost of production is the sum of the variable costs (cost of the natural gas feed in /year and the operating
costs of the plant (pump and compressor power requirements, cooling and heating duties, etc.) and other
production costs including direct production costs, overheads, general expenses.
The cost of operating a compressor for a year was calculated by multiplying the power requirement of the
compressor in MW by the price of electricity in /MJ (taken to be 3.25p/MJ as per the remit), then multiplying by the
number of seconds per year. Using the first CO2 compressor in Design 1 as an example, which has a power
requirement of 2.08 MW:
=
= 2.08 0.0325 3600 8000
= 1.95
C-2-1
Summing up the annual operating cost of the major process equipment gives the annual equipment cost portion of
the variable costs; the other portion regards the quantity of natural gas feed taken into the process. Table C-2-1
gives the Total Annual Operating Cost of the plant:
Table C-2-1: Total Annual Operating Cost of the Plant
Annual Operating Cost (M/year)

11.8

7.44
Table C-2-2 gives the flowrates of natural gas for the two designs, and the estimated price of natural gas for the
project duration. The annual cost of the gas is simply calculated by multiplying the two together. It should be noted
that 100 % operating capacity was assumed whenever the plant is running.
Table C-2-2: Natural Gas Consumption of the Two Designs
Natural Gas Consumed (tonne/year)
Cost of Natural Gas (/tonne)
Annual Cost of Feed Gas (M/year)

162,000
160
25.9

117,000
160
18.7
Table C-2-3 Total Variable Costs (Annual Operating Cost + Cost of Feed Gas)
Annual Variable Costs (/year)

37.7

26.1
70
GROUP 1

The Total Cost of Production must take into account the following parameters:
Volume 1
Table C-2-4: Total Cost of Production

All in (M/year)
Direct Production Costs
Variable Costs
Operating Labour (0.02 *
FCI)
Supervision (0.2 * Operating
Labour)
Maintenance (0.05 * FCI)
Supply (0.15 * Maintenance)
Laboratory (0.15 * Operating
Labour)
Fixed Manufacturing
Taxes and Insurance (0.03 *
FCI)
Overheads (0.6*(Operating Labour + Supervision +
Maintenance))
General Expenses
Admin (0.15*(OL + M + S))
Distribution and Selling
R&D
Annualised Capital
Total Cost of Production
Design 1 (SMR with MEA

CC)
37.7
1.74
Design 2 (Membrane SMR

with CLC)
26.1
1.13
0.348
0.226
4.35
0.652
0.261
2.82
0.423
0.169
2.61
1.69
3.86
2.50
0.966
2.00
1.00
6.96
63.9
0.626
2.00
1.00
4.51
44.7
C-3: Revenue estimate

The price range of hydrogen from 1997 to 2002 was found to vary from 715 - 3150 /tonne in todays money. Other
sources came to a consistent figure of 2250/tonne in todays money and so this was established as the median
(P50) value. However, market research suggests future prices will be more favourable than that, so a mode price of
2600/tonne was chosen, and the lowest limit of 715/tonne was disregarded as being very unlikely to occur at 1%.
The result of this led to the upper P10 limit of 3170/tonne and lower P90 limit of arbitrarily chosen 1700/tonne.
Using Swansons rule, the expected price of hydrogen can be calculated:
= (0.3 10) + (0.4 50) + (0.3 90)
= (0.3 3170) + (0.4 2250) + (0.3 1700) =
2360
C-3-1
As for CO2, an average price of 8.09/tonne from literature was used.

The following table of product H2 and by-product CO2 revenue can be constructed:
Table C-3-1: Plant Revenues
Variable
Hydrogen Produced (tonnes/year)
Cost of Hydrogen (/tonne)
Hydrogen Revenues (M/year)
CO2 Produced (tonnes/year)
Cost of CO2 (/tonne)
CO2 Revenues (M/year)
Total Revenues (M/year)

41,800
2360
98.6
411,700
8.09
3.33
102.0

41,800
2360
98.6
298,000
8.09
2.41
101.1
71
GROUP 1

Volume 1
It is evident that the total revenues of the processes are very similar since they were designed to produce the same
quantity of hydrogen, as stated in the remit, of 5 tonnes/hour. Furthermore, the revenue generated by the byproduct CO2 is much smaller than that of the primary product hydrogen, as is expected.
C-4: Net Profit

Annual net profit is very simply determined from the following equation:
C-4-1
=
Table C-4-1: Annual Profits of the Two Proposed Plants
Variable
Net Profit (/year)

38.1

56.4
C-5: Calculating Depreciation

Depreciation was calculated using a declining balance method.
Table C-5-1 and C-5-2: Depreciation over 20 years of the proposed plants.
Design 1
Design 2
Year
0
1
2
3
4
5
6
7
8
Book Value
Depreciation []
86,995,611
78,296,050
70,466,445
63,419,800
57,077,820
51,370,038
46,233,034
41,609,731
37,448,758
0
8,699,561.07
7,829,604.96
7,046,644.46
6,341,980.02
5,707,782.02
5,137,003.81
4,623,303.43
4,160,973.09
33,703,882
3,744,875.78
10
11
12
13
14
15
30,333,494
27,300,144
24,570,130
22,113,117
19,901,805
17,911,625
3,370,388.20
3,033,349.38
2,730,014.44
2,457,013.00
2,211,311.70
1,990,180.53
16
16,120,462
1,791,162.48
17
14,508,416
1,612,046.23
18
13,057,574
1,450,841.61
19
11,751,817
1,305,757.45
20
10,576,635
1,175,181.70
Total
76,418,975
Year
Book Value
Depreciation []
0
1
2
3
4
5
6
7
8
56,426,085
40,062,520
28,444,390
20,195,517
14,338,817
10,180,560
7,228,198
5,132,020
3,643,734
0
16,363,564.70
11,618,130.94
8,248,872.97
5,856,699.81
4,158,256.86
2,952,362.37
2,096,177.28
1,488,285.87
9
10
11
12
13
14
15
2,587,051
1,836,806
1,304,133
925,934
657,413
466,763
331,402
1,056,682.97
750,244.91
532,673.88
378,198.46
268,520.91
190,649.84
135,361.39
16
235,295
96,106.59
17
167,060
68,235.68
18
118,612
48,447.33
19
20
84,215
59,793
34,397.60
24,422.30
Total
56,366,293
72
GROUP 1

=
Volume 1
C-5-1
= 1,2,3 20
Dk is the depreciation in year k; Fd = 2/N where N is the project lifetime, so in this case Fd = 2/20 = 0.1; FCI is the fixed
capital investment and the sum of Dj means the sum of the depreciations in previous years.
C-6: Calculating the NPV, DCFRoR and Profitability Index

Table C-6-1 and C-6-2 show the calculated values for the discounted cumulative cash flow using the expected value
for the hydrogen price. This data is used to plot figures 9-1 and 9-2. Note that all values have been discounted into
the value of money in 2018 (year 2) the time where plant operation begins.
Table C-6-1: Economic Analysis of Design 1 (All values in M )

Ye
ar
0
0.5
1
1.5
2
3
4
5
6
7
8
Gross
Profit
-8.70
-17.40
-26.10
-26.10
-9
23
38.04
38.04
38.04
38.04
38.04
Depreciation
Charge
0
0
0
0
0
8.70
7.83
7.05
6.34
5.71
5.14
Taxable
Income
0
0
0
0
0
0
30
31
32
32
33
Taxes
Paid
0
0
0
0
0
0
0
11
11
11
11
Cash
Flow
-9
-17
-26
-26
-9
23
38
27
27
27
27
9
10
11
12
13
14
15
16
17
18
19
20
38.04
38.04
38.04
38.04
38.04
38.04
38.04
38.04
38.04
38.04
38.04
38.04
4.62
4.16
3.74
3.37
3.03
2.73
2.46
2.21
1.99
1.79
1.61
1.45
33
34
34
35
35
35
36
36
36
36
36
37
12
12
12
12
12
12
12
12
13
13
13
13
27
26
26
26
26
26
26
26
25
25
25
25
Discount
Factor
1.00
0.96
0.93
0.89
0.86
0.79
0.74
0.68
0.63
0.58
0.54
0.50
0.46
0.43
0.40
0.37
0.34
0.32
0.29
0.27
0.25
0.23
0.21
Present Value
of CF
-9
-17
-24
-23
-7
18
28
19
17
16
14
Cum. CF
[]
-9
-25
-50
-73
-80
-62
-34
-16
2
17
32
13
12
11
10
10
9
8
7
7
6
6
5
45
57
68
79
88
97
105
113
120
126
132
137
73
GROUP 1

Volume 1
Table C-6-2: Economic Analysis of Design 2 (All values in M )

Ye
ar
0
0.5
1
1.5
2
3
4
5
6
7
8
Gross
Profit
-5.64
-11.29
-16.93
-16.93
-6
34
56.29
56.29
56.29
56.29
56.29
Depreciation
Charge
0
0
0
0
0
16.36
11.62
8.25
5.86
4.16
2.95
Taxable
Income
0
0
0
0
0
0
45
48
50
52
53
Taxes
Paid
0
0
0
0
0
0
0
16
17
18
18
Cash
Flow
-6
-11
-17
-17
-6
34
56
41
39
39
38
9
10
11
12
13
14
15
16
17
18
19
20
56.29
56.29
56.29
56.29
56.29
56.29
56.29
56.29
56.29
56.29
56.29
56.29
2.10
1.49
1.06
0.75
0.53
0.38
0.27
0.19
0.14
0.10
0.07
0.05
54
55
55
56
56
56
56
56
56
56
56
56
19
19
19
19
19
20
20
20
20
20
20
20
38
37
37
37
37
37
37
37
37
37
37
37
Discount
Factor
1.00
0.96
0.93
0.89
0.86
0.79
0.74
0.68
0.63
0.58
0.54
0.50
0.46
0.43
0.40
0.37
0.34
0.32
0.29
0.27
0.25
0.23
0.21
Present Value
of CF
-6
-11
-16
-15
-5
27
41
28
25
23
21
Cumulativ
e CF
-6
-17
-32
-47
-52
-25
16
44
69
91
112
19
17
16
15
14
13
12
11
10
9
8
8
131
148
164
178
192
205
216
227
237
246
254
262
An explanation of the table shall be provided here. It is assumed for the first two years of the project, the equipment
is being bought and installed; this phase is where capital is being spent and no revenue is being made. Production
begins in year 2, at which point depreciation of the equipment begins. It is predicted the plant starts to make profit
in year 3; this first year is tax-free. Henceforth, taxation occurs at 35 % of (profit-depreciation). The cash flow is equal
to the gross profit for the year minus the taxes paid for the year. The discount factor is a complicated expression
which allows the cash flow in year x to be converted to the value of the money at the start of the project, in 2018.
The discount factor can be expressed as:
=
1
(1 + )
C-6-1
i is the interest rate and it takes into account the rate of return on the loan the investors gave to Costain; it has been
assigned a high value of 10% for this economic analysis as a test for the economic performance of the plant.
However, inflation must also be accounted for; the general trend obtained from the CEPCI chart was that inflation is
increasing every year at approximately 2% per annum; thus i is amended by 0.1 0.02 = 0.08. So the final settled
value for i was 0.08.
74
GROUP 1

Volume 1
The present value CF is simply the ordinary cash flow multiplied by the discount factor; the cumulative cash flow is
the sum of the net present cash flows.
The NPV is the total cumulative cash flow after 20 years; for design 1, this is 137 million; for design 2, 262 million.
The Payback Period is the time taken for the project to break even; in other words, for the NPV to transition above 0.
The discounted cumulative cash flow rate of return (DCFRoR) is the maximum value of i in equation C-6-1 until the
project has just broken even at the end of 20 years. This was found iteratively; but for design 1, the DCFRoR is 0.25
and for design 2, 0.41. As i increases, the return of investment increases, and capital is being spent more efficiently.
The Profit to Investment ratio (or Profitability Index) is simply the NPV divided by the Fixed Capital Investment. A
higher Profitability Index suggests the project is worthwhile investing in.
Figure C-6-1: CEPCI chart used in the calculation of inflation rates. 2018 was estimated to be 650.
75
GROUP 1

Volume 1
Table C-1-1: Purchasing and Installation Costs for Design 1
Part Of Process
Name
0.063
774
1,548
E-101
60.320
1,524
4.8
7,314
T-101
SulfaTreat Beds
2.5 x 6
169,127
676,508
R-201
Pre-Reformer
1.9x6.65
19,600
78,400
R-202
2x12
1,677,000
6,708,000
1.4 x 3.08
23,524
94,096
1.4 x 4
31,040
124,161
5 x 10
280,583
3.5
982,042
Estimated
50,000
3.5
175,000
E-201
SMR Reactor
High Temp WGS
Reactor
Low Temp WGS
Reactor
Steam Drum
Water KnockOut Drum
Gas Cooler
350
6,251
4.8
30,005
E-202
BFW Heater
250
5,108
4.8
24,520
E-203
20
1,122
4.8
5,387
1000
11,736
4.8
56,332
E-205
Gas Trim Cooler

Low Temp WGS
Cooler
Furnace
12 m high
4,576,696
4.8
21,968,138
E-206
Backup Heater
50.000
1,945
4.8
9,336
P-201
Gas Expander
Unsized
negligible
N/A
P-202
Pump
100
18,479
129,350
R-203
R-204
V-201
V-202
SMR + WGS
Quantity Purchase Cost [] Wroth Factor Installation Cost []
Backup Feed
Compressor
Feed Heater
P-101
Desulphurisation
Description
V, T, R: Dimensions [D x L] in m. E: Heat Transfer Area

in m2. Compressor: Power Rating in MW. Pump: Flow
in litres/s
E-204
76
GROUP 1
PSA
P-203
Pump
T-301
PSA Towers
Absorption
Column
Stripping
Column
Stack
Water-Gas
Separator
Surge Drum
T-401
T-402
T-403
V-401
V-402
V-403
E-401
Carbon Capture
E-402
E-403
E-404
E-405
P-401
P-402
P-403
P-404
V-501
CO2
Compression
V-502
E-501
E-502
Reflux Drum
First Furnace
Gas Cooler
Second Furnace
Gas Cooler
Reboiler
Rich/Lean
Exchanger
Flue Gas Cooler
Flue
Compressor
First Lean Pump
Second Lean
Pump
Reflux Pump
Water KnockOut Drum
CO2 Hold-Up
Tank
Stripper Gas
Cooler
Backup Water

5
2
Volume 1
1,254
8,779
2.5 x 6
904,283
3,617,132
4.8 x 20.8
665,500
2,662,000
0.5 x 7.2
18,010
72,040
Estimated; 80 m high, concrete
1,000,000
2,000,000
Estimated
50,000
3.5
175,000
5 x 13
148,000
3.5
518,000
Estimated
50,000
3.5
175,000
Estimated
50,000
4.8
240,000
1464.000
14,752
4.8
70,808
Estimated
250,000
4.8
1,200,000
60.000
2,170
4.8
10,415
8000.000
40,867
4.8
196,161
5.678
16,465
32,929
68
13,086
91,601
68
26,172
183,201
57
22,290
156,029
Estimated
50,000
3.5
175,000
4 x 11
75,000
3.5
262,500
Estimated
150,000
4.8
720,000
2.000
282
4.8
1,353
77
GROUP 1

Volume 1
Heater
E-503
Cooler #1
3.164
290
4.8
1,394
E-504
Cooler #2
3.407
315
4.8
1,511
E-505
Cooler #3
7.050
714
4.8
3,428
P-501
Compressor #1
9,018
18,036
P-502
Compressor #2
2.082
2.093
9,047
18,094
P-503
Compressor #3
1.209
Liquid CO2
14.219
Pump
TOTAL Inside Battery Limits Costs
6,509
13,018
6,400
44,800
P-504
10,454,932
43,738,366
Table C-1-2 Purchasing and Installation Costs for Design 2

Purchasing and Installation Costs
Part Of Process
Name
P-101
Desulphurisation
SMR Membrane with

CLC
E-101
T-101
R-201
R-202
R-202a
R-203
V-201
Description
Backup Feed
Compressor
Feed Heater
SulfaTreat Beds
Pre-Reformer
Fuel Reactor
SMR in Fuel
Raeactor
Air Reactor
Water
Condenser
V, T, R: Dimensions [D x L] in m. E: Heat
Transfer Area in m^2. Compressor: Power
Rating in MW. Pump: Flowrate in l/s
Quantity Purchase Cost [] Wroth Factor Installation Cost []
0.063
774
1,548
60.320
2.5 x 6
1.9x6.65
2.9 x 9.8
1
2
1
1
2,177
101,430
19,600
31,500
4.8
4
4
4
10,448
405,720
78,400
126,000
2x9.8
6,380,000
25,520,000
3.1 x 10
37,100
148,400
Estimated
50,000
3.5
175,000
78
GROUP 1

E-301
Water
Condenser
Pre-Reformer
Heater
Pre-SMR Heater
Fuel Reactor
Pre-Heater
CLC Flue Gas
Cooler
Membrane
Cooler
Membrane Flue
Gas Cooler
Compressed Air
Cooler
Make Up Gas
Expander
Make Up Air
Compressor
Cyclone
Water
Condenser
CO2 Hold-Up
Tank
CO2 Condenser
P-301
CO2 Compressor
0.77
4,965
9,930
P-302
CO2 Pump
14
6,311
44,180
28
7,088,300
V-202
E-201
E-202
E-203
E-204
E-205
E-206
E-207
P-201
P-202
C-201
V-301
Product Separation
and Compression
Volume 1
V-302
TOTAL Inside Battery Limits Costs
Estimated
50,000
3.5
175,000
Estimated
50,000
4.8
240,000
Estimated
20,000
4.8
96,000
Estimated
100,000
4.8
480,000
720
9,636
4.8
46,255
2400
19,845
4.8
95,254
720
9,636
4.8
46,255
27
1,344
4.8
6,450
Estimated
10,000
20,000
2.077
9,005
18,010
Estimated
2,000
12,000
Estimated
100,000
3.5
350,000
4x9
66,204
3.5
231,713
400
6,773
4.8
32,508
28,369,072
79
GROUP 1

Volume 1
Appendix D: Mass and Energy Balance Sample

Calculations
1. Individual Unit balance for Design 1
Please refer to the Appendix E for individual stream data.
Table D-1: Desulphurisation
Energy n
1
U1
Total
Energy in
E-101

MW
Energy out
-1
-1.66 x10
U2
0
3
-1
-1.66 x10
Total
MW
Energy out
2.23 x10-1
P-101
Overall Balance
MW
1.04x10-7
5.70x10-2
5.70x10-2
MW
0
Overall
0 MW
0%
The table above contains the inlet and outlet energy streams, plus the energy generated by equipment in the
Desulphurisation section.
Table D-2: Furnace
MW
Energy out
MW
-2
3.7 x10
4a
4.49
1.49 x101
7a
4.40 x101
4.40 x101
8
4.99 x101
-5.47 x10-1
16
3.30 x101
1
5.839 x10
Total
1.314 x102
Energy in
MW
Energy out
MW
Heat produced by
Heat lost to the
1.19 x102
-2.38 x101
furnace
surroundings
Heat generated by reactions
Pre-reformer
2.67 x10-1 MW
SMR
5.83 MW
Overall Balance
Overall
-2.21 x101 MW
-12.5%
The table above contains the inlet and outlet energy streams, plus the energy generated by reactions and equipment
in the Furnace section.
Energy in
4
7
7a
15
Total
80
GROUP 1

Table D-3: Water Gas Shift
Volume 1

MW
Energy out
4.99 x101
10a
1
4.99 x10
Total
MW
Energy out
E-201
E-202
E-203
Heat Generated from reaction
Energy in
8
Total
Energy in
HWGS
LWGS
MW
2.06 x10-1
2.06 x10-1
MW
-3.34 x101
-1.15 x101
-1.13 x101
4.38
2.18
Overall Balance
Overall
0 MW
0%
The table above contains the inlet and outlet energy streams, plus the energy generated by reactions and equipment
in the water gas shift section.
Table D-4: PSA
MW
Energy out
-1
1.57 x10
12
13
1.57 x10-1
Total
Overall Balance
Energy in
11
Total
MW
1.04 x10-1
5.30 x10-2
1.57 x10-1
Overall
0 MW
0%
The table above contains the inlet and outlet energy streams in the PSA section.
Table D-5: Summary of Energy Balance Errors in Design 1
Unit
Percentage error (%)
Desulphurisation
0.00
Furnace
12.5
WGS
0.00
PSA
0.00
OVERALL
12.5
The table above contains the error in the energy balance for each section
2. Furnace Energy Balance Explanation

The two methods used are both based on the energy equation:
D-1-1
=
Where is the molar flowrate of the component in kmol/h; is the temperature difference between the stream
and a reference temperature. The reference temperature was selected to be 298K.
Method 1
81
GROUP 1

Volume 1
For calculations in the design of the furnace, the difference in energy between 2 streams is accounted by:
= ( )
D-1-2
Method 2
The energy balance for the rest of Design 1 and Design 2 (bar MEA) was calculated with:
D-1-3
Table D-6: Summary of Calculated Energy Differences Using Methods 1 & 2

Method 1
Method 2
Percentage error
Preheat PR (Stream 4a
Stream 4)
2.78 MW
4.45 MW
37.5 %
Preheat SMR (Stream 7a

Stream 7)
1.91 x101 MW
2.91 x101 MW
34.3 %
Outlet heat (Stream 16

Stream 15)
2.58 x101 MW
3.30 x101 MW
21.8 %
Total
4.77 x101 MW
6.66 x101 MW
28.4 %
1.89 x101 MW
Difference
3. Sample Calculations for Designs 1 & 2

Enthalpy Calculations
For vapour streams
Individual component enthalpy is calculated using the equations from Sinnott.
The specific heat is calculated using:
D-1-4
= + + +
Where Cp is the specific heat in kJ/kmolK, the constants a, b, c and d are obtained from Appendix C in Sinnott.
The enthalpy of each component is calculated using Equation D-1-1.
The following sample calculation uses Methane from Stream 1 in Design 1. Please refer to Appendix E for data
utilised.
The constants for methane are a = 19.251; b = 52.126x10-3; c = 11.974x10-6; d = 1.132x10-8
The stream temperature is 283 K.
= 19.251 + 52.126 10
283 + 11.974 10
283 + 1.132 10
283 = 34.71
Using = 911.2 kmol/h

= 911.2 34.71 (283 298) = 4.74 10
Converting to Watts
82
GROUP 1

1000
= 4.74 10
= 1.32 10
3600
Volume 1
For two phase streams

For all the streams containing both vapour and liquid (mainly water) the enthalpy was calculated as above with the
addition of the latent heat of the water being considered.
As a sample calculation stream 8a from design 2 will be used.
Using the method above for vapour, the enthalpy of water in stream 8a should be:
T = 298.01 K; a = 32.243, b = 19.238 10 , c = 10.55 10 , d = + 3.596 10
= 32.243 + 19.238 10
298.01 + 10.55 10
298.01 + 3.596 10
298.01 = 33.66
Using = 5950 kmol/h

= 5950 33.66 (298.01 298) = 2.00 10
Converting to Watts
= 2.00 10
1000
= 5.56 10
3600
The value obtained is for the vapour phase of the water, thus to obtain the total enthalpy the latent heat of water
were added. At 303K the value for the latent heat capacity of water is 39628.8 J/molK
= 5.56 10 + 39628.8 5950
1000
= 6.55 10
3600
3.1 Design 1
=
D-1-5
kg
= 2.25 10 220 10 = 4.82 10
The percentage error of the overall mass balance

% difference =

2.25 10 220 10
100 =
100 = 2.19%

220 10

The energy balance was defined as:
= + +
= ++
= (
D-1-6
+ + )
= 1.31 10 5.84 10 (1.19 10 2.38 10 ) = 2.214 10

100

2.21 10
% =
100 = 12.5
5.84 10 + 1.19 10
D-1-7
83
GROUP 1

Volume 1
3.2 Design 2
Equation D-1-5 was again used.
= = 1.97 10 1.99 10 = 1.92 10
kg
The percentage error of the overall mass balance

% error =

1.97 10 1.99 10
100 =
100 = 0.97%

1.99 10

Equations D-1-6 and D-1-7 were utilised.
= (
+ + )
= 6.88 10 3.93 10 (2.12 10 1.32 10 + 1.29) = 1.23

=
1.23
100 = 2.03 %
3.93 10 + 2.12 10
84
GROUP 1

Volume 1
Appendix E: Individual Mass and Energy Balance

Mass Balance for individual streams (Design 1)
Component | Stream No.
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
MEA
Temperature (K)
Pressure (bar)
Total
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
1
1.46x104
2.63 x103
1.16x103
2.52 x102
1.26 x102
7.48 x101
8.93 x101
2
9.54 x10
2.90 x102
0
0
-1
1 x10
0
0
0
283
33
2.02 x104
8
2
2.75 x10
0
0
0
1a
1.46x104
2.63 x103
1.16x103
2.52 x102
1.26 x102
7.48 x101
8.93 x101
2
9.54 x10
2.90 x102
0
0
-1
1 x10
0
0
0
283
33
2.02 x104
8a
2
2.75 x10
0
0
0
1b
1.46x104
2.63 x103
1.16x103
2.52 x102
1.26 x102
7.48 x101
8.93 x101
2
9.54 x10
2.90 x102
0
0
-1
1 x10
0
0
0
303
33
2.02 x104
9
2
2.75 x10
0
0
0
2
1.46x104
2.63 x103
1.16x103
2.52 x102
1.26 x102
7.48 x101
8.93 x101
2
9.54 x10
2.90 x102
0
0
-1
1 x10
0
0
0
303
33
2.02 x104
9b
2
2.75 x10
0
0
0
3
1.46x104
2.63 x103
1.16x103
2.52 x102
1.26 x102
7.48 x101
8.93 x101
2
9.54 x10
2.90 x102
0
0
-1
1 x10
0
0
0
303
32.93
2.02 x104
10
2
2.75 x10
0
0
0
Mass of the stream (kg/h)

4
4a
5
3
3
9.47x10
9.47x10
9.47x103
1.71 x103 1.71 x103 1.71 x103
7.50 x102 7.50 x102 7.50 x102
1.65 x102 1.65 x102 1.65 x102
8.24 x101 8.24 x101 8.24 x101
4.77 x101 4.77 x101 4.77 x101
5.7 x101
5.7 x101
5.7 x101
2
2
2
6.24 x10
6.24 x10
6.24 x10
1.85 x102 1.85 x102 1.85 x102
3
0
0
5.37 x10
0
0
0
0
0
0
5a
9.47x103
1.71 x103
7.50 x102
1.65 x102
8.24 x101
4.77 x101
5.7 x101
2
6.24 x10
1.85 x102
3
5.37 x10
0
0
6
1.19 x104
0
0
0
0
0
0
3
2.17 x10
1.85 x102
3
4.10 x10
1
1.97 x10
0
7
1.19 x104
0
0
0
0
0
0
3
2.17 x10
1.85 x102
3
4.10 x10
1
1.97 x10
0
7a
1.19 x104
0
0
0
0
0
0
3
2.17 x10
1.85 x102
3
4.10 x10
1
1.97 x10
0
0
0
0
303
32.93
1.31x104
10a
2
2.75 x10
0
0
0
0
0
0
673
32.93
1.85x104
13
2
2.75 x10
0
0
0
6.62 x10
0
0
688
30
1.85x104
14
2
2.75 x10
0
0
0
6.62 x10
0
0
688
30
5.86 x104
15
3
5.42 x10
9.25 x102
4.13 x102
8.72 x101
6.62 x10
0
0
1223
30
5.86 x104
16
0
0
0
0
0
0
0
303
32.93
1.31x104
11
2
2.75 x10
0
0
0
0
0
0
673
32.93
1.85x104
12
0
0
0
0
85
GROUP 1
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
MEA
Temperature (K)
Pressure (bar)
Total

Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide, H2S
Hydrogen , H2
0
0
0
8.76 x103
1.85 x102
4
2.85 x10
1.62 x104
0
0
0
0
8.76 x103
1.85 x102
4
2.85 x10
1.62 x104
0
0
0
0
2.44 x104
1.85 x102
4
2.21 x10
6.19 x103
0

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4
4
4
4
0
2.44 x10 3.23 x10
3.23 x10
3.23 x10
2
2
2
2
0
1.85 x10 1.85 x10
1.85 x10
1.85 x10
4
4
4
0
2.21 x10 1.88 x10
1.88 x10
0.00
3
3
3
3
0
6.19 x10 1.18 x10
1.18 x10
1.18 x10
0
0
0
0
0
4.76 x103
0
0
1295
29.88
5.86x104
4.76 x103
0
0
675
29.78
5.86x104
5.48 x103
0
0
757
29.3
5.86x104
5.48 x103
0
0
513
29.1
5.86x104
16a
0
0
0
0
0
0
0
5.39 x104
1.19 x105
4
2.02 x10
0
0
0
17
0
0
0
0
0
0
0
5.39 x104
1.19 x105
3
8.0 x10
0
0
0
17a
0
0
0
0
0
0
0
5.39 x104
1.19 x105
3
8.0 x10
0
0
0
17b
0
0
0
0
0
0
0
5.39 x104
1.19 x105
3
8.0 x10
0
0
0
5.84 x103
0
0
558.1
28.4
5.86x104
5.84 x103
0
0
303
25
5.86x104
5.84 x103
0
0
303
25
3.98x104
Volume 1
5.23x103
0
0
303
25
5.23x103

18
19
19a
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4
5.39 x104
6.24 x10
6.24 x104
0
1.19 x105 0
3
5
5
2.48 x10
4.14 x10
4.14 x10
0
0
0
0
0
0
0
0
0
0
0
0
3.23 x104
1.85 x102
0
1.18 x103
0
0
0
0
3.23 x104
1.19 x105
0
1.18 x103
0
4.36 x101
1
2.71 x10
3.23 x101
3.26 x104
1.19 x105
0
1.18 x103
0
0
0
0
5.39 x104
1.19 x105
4
2.02 x10
0
0
6.1 x102
0
0
303
1
3.46 x104
6.1 x102
3.6 x104
0
303
1
1.89 x105
6.1 x102
3.6 x104
0
288.55
1
1.96 x105
0
3.27 x103
0
787.17
1
1.96 x105
20
0
0
0
0
0
0
0
5.16 x104
6.32
5
5.69 x10
0
0
0
21
0
0
0
0
0
0
0
5.12
0
5
1.96 x10
0
0
0
21a
0
0
0
0
0
0
0
5.12
0
5
1.96 x10
0
0
0
22
0
0
0
0
0
0
0
3.30 x104
0
5
5.82 x10
0
0
0
86
GROUP 1
Oxygen, O2
MEA
Temperature (K)
Pressure (bar)
Total
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen , H2
Oxygen, O2
MEA
Temperature (K)
Pressure (bar)
Total
3.27 x103
0
313
1
1.96 x105
23
0
0
0
0
0
0
0
4
2.23 x10
0
5.38 x105
0
0
0
0
1.88 x105
393
1
7.48 x105
3.27 x103
0
313
1
1.84 x105
24
0
0
0
0
0
0
0
4
1.07 x10
0
4.35 x104
0
0
0
0
1.83 x105
393
1
2.37 x105
3.27 x103
0
381
3.1
1.84 x105
24a
0
0
0
0
0
0
0
4
1.07 x10
0
4.35 x104
0
0
0
0
1.83 x105
364
1
2.37 x105

Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
28a
0
0
0
0
0
0
0
29
0
0
0
0
0
0
0
29a
0
0
0
0
0
0
0

0
0
3.27 x103
3275.35
5
5
0
0
1.83 x10
1.83 x10
313
313.15
334
334
3.1
3.1
1.5
1
5
5
5
1.84 x10
1.79 x10
6.60 x10
6.60 x105
25
25a
25b
25c
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4
4
4
4
1.12 x10
1.12 x10
1.12 x10
1.12 x10
0
0
0
0
5
5
5
4.3 x10
4.3 x10
4.3 x10
4.3 x105
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
5
5
5
1.84 x10
1.84 x10
1.84 x10
1.84 x105
319
319
319
319
1
3.1
3.1
3.1
5
5
5
6.25 x10
6.25 x10
6.25 x10
6.25 x105
29b
29c
29d
29e
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Volume 1
0
3
2.08 x10
371
1
6.23 x105
26
0
0
0
0
0
0
0
3
2.74x10
5
1.19 x10
1.88 x104
0
0
0
3
3.28 x10
3.13 x102
343
1.5
1.44 x105
0
3
1.85 x10
371
1
1.99 x105
26a
0
0
0
0
0
0
0
3
2.74x10
5
1.19 x10
1.88 x104
0
0
0
3
3.28 x10
3.13 x102
298
1
1.44 x105
0
3
1.85 x10
371
1
1.99 x105
27
0
0
0
0
0
0
0
3
2.74x10
5
1.19 x10
1.72 x103
0
0
0
3
3.28 x10
4.9 x10-1
298
1
1.27 x105
0
5
3.71 x10
376
1
9.85 x105
28
0
0
0
0
0
0
0
4
5.146 x10
6.29
3.7 x105
0
0
0
0
2.23 x102
371
1
4.22 x105
29f
0
0
0
0
0
0
0
29g
0
0
0
0
0
0
0
30
0
0
0
0
0
0
0
U1
0
0
0
0
0
0
0
87
GROUP 1
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen , H2
Oxygen, O2
MEA
Temperature (K)
#Pressure (bar)
Total
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen , H2
Oxygen, O2
MEA
Temperature (K)
Pressure (bar)
Total
5.15 x104
6.29
3.7 x105
0
0
0
0
2
2.23 x10
298
1
5
4.22 x10
U2
0
0
0
0
0
0
0
0
0
0
0
-1
1 x10
0
0
0
303
33
1 x10-1
5.15 x104
6.29
0
0
0
0
0
0
298
1
4
5.15 x10
U3
0
0
0
0
0
0
0
0
0
3
5.37 x10
0
0
0
0
0
673
32.93
5.37 x103
5.15 x104
6.29
0
0
0
0
0
0
468
5
4
5.15 x10
U4
0
0
0
0
0
0
0
0
0
4
4.02 x10
0
0
0
0
0
688
30
4.02 x104

5.15 x104
5.15 x104 5.15 x104
5.15 x104
6.29
6.29
6.29
6.29
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
298
474
298
393
5
25
25
70
4
4
4
4
5.15 x10
5.15 x10
5.15 x10
5.15 x10
U5
U6
U6a
U7
0
5.14 x13
5.14 x13
0
2
2
0
0
9.25 x10
9.25 x10
2
2
0
0
4.13 x10
4.13 x10
1
1
0
0
8.72 x10
8.72 x10
1
1
0
0
4.36 x10
4.36 x10
1
1
0
0
2.71 x10
2.71 x10
1
1
0
0
3.23 x10
3.23 x10
2
2
0
0
3.3 x10
3.3 x10
2
2
5
0
1.05 x10
1.05 x10
1.19 x10
4
0
0
0
1.88 x10
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3.6 x104
0
0
0
0
303
303
303
283
25
32.93
1
1
4
3
3
1.88 x10
7.11 x10
7.11 x10
1.55x105
Volume 1
5.15 x104
6.29
0
0
0
0
0
0
293
70
4
5.15 x10
U8
0
0
0
0
0
0
0
0
0
4
1.22 x10
0
0
0
0
0
313.15
3.1
1.22 x104
5.15 x104
6.29
0
0
0
0
0
0
293
70
4
5.15 x10
U9
0
0
0
0
0
0
0
0
0
3
5.5 x10
0
0
0
0
0
313.15
3.1
5.52 x103
5.15 x104
6.29
0
0
0
0
0
0
293
71
4
5.15 x10
R1
0
0
0
0
0
0
0
5.18 x102
0
5
3.7 x10
0
0
0
0
2
2.23 x10
298
1
3.7 x105
0
0
0
0
0
0
0
0
303
33
0.00
R1a
0
0
0
0
0
0
0
5.18 x102
0
5
3.7 x10
0
0
0
0
2
2.23 x10
313
1
3.7 x105
88
GROUP 1

Volume 1

Component | Stream
Stream No.
No. R2
R3
Methane, CH4
0
0
Ethane, C2H6
0
0
Propane, C3H8
0
0
n-Butane, C4H10
0
0
i-Butane, C4H10
0
0
n-Pentane, C5H12
0
0
n-Hexane, C6H14
0
0
Carbon Dioxide, CO2
0
5.18 x102
Nitrogen, N2
0
0
4
Water, H2O
1.7 x10
3.87 x104
Carbon Monoxide, CO
0
0
Hydrogen Sulphide, H2S 0
0
Hydrogen , H2
0
0
Oxygen, O2
0
0
2
MEA
3.12 x10
5.36 x102
Temperature (K)
298
313
Pressure (bar)
1
1
4
4
Total
1.73 x10
3.88 x10
89
GROUP 1

Volume 1
Mass Balance for individual streams (Design 2)

Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
Nickel Oxide
Nickel
Temperature (K)
Pressure (bar)
Total

4
4a
5
8.53 x103 8.53 x103 8.53 x103
1.53 x103 1.53 x103 1.53 x103
6.75 x102 6.75 x102 6.75 x102
2
2
2
1.48 x10
1.48 x10
1.48 x10
1
1
7.40 x10
7.40 x10
7.40 x101
4.30 x101 4.30 x101 4.30 x101
1
1
1
5.10 x10
5.10 x10
5.10 x10
5.62 x102 5.62 x102 5.62 x102
2
2
2
1.67 x10
1.67 x10
1.67 x10
3
4.83x10
0
0
1
1.06 x104
1.90 x103
8.38 x102
2
1.86 x10
9.30 x101
5.10 x101
1
6.00 x10
6.95 x102
2
2.07 x10
0
1a
1.06 x104
1.90 x103
8.38 x102
2
1.86 x10
9.30 x101
5.10 x101
1
6.00 x10
6.95 x102
2
2.07 x10
0
1b
1.06 x104
1.90 x103
8.38 x102
2
1.86 x10
9.30 x101
5.10 x101
1
6.00 x10
6.95 x102
2
2.07 x10
0
2
1.06 x104
1.90 x103
8.38 x102
2
1.86 x10
9.30 x101
5.10 x101
1
6.00 x10
6.95 x102
2
2.07 x10
0
3
1.06 x104
1.90 x103
8.38 x102
2
1.84 x10
9.20 x101
5.30 x101
1
6.40 x10
6.96 x102
2
2.07 x10
0
1.80 x10
0
0
0
0
0
283
33
1.46 x104
8a
0
0
0
0
0
0
0
0
0
303
33
1.46 x104
9
0
0
0
0
0
0
0
0
0
303
32.9
1.46 x104
10
0
0
0
0
0
0
0
0
0
303.00
32.93
1.46x104
11
2.82 x102
0
0
0
0
0
0
0
0
303
32.93
1.18x104
11a
2.82 x102
0
0
0
0
0
0
0
0
673
32.83
1.18x104
12
2.82 x102
0
0
0
0
0
0
0
0
673
32.93
1.66x104
13
0
0
0
0
0
6 x101
0
0
0
688
25
1.66x104
14
2.23 x103
3.69 x102
2
1.63 x10
3.50 x101
0
0
0
0
0
283
33
1.46 x104
Component | Stream No. 8
Methane, CH4
0
Ethane, C2H6
0
Propane, C3H8
0
n-Butane, C4H10
0
6
10734
0
0
0
0
0
0
1.95 x103
2
1.67 x10
3.69 x103
1
6a
10734
0
0
0
0
0
0
1.95 x103
2
1.67 x10
3.69 x103
6b
10734
0
0
0
0
0
0
1.95 x103
2
1.67 x10
3.69 x103
1.80 x10
0
6 x101
0
0
0
672.6
25
1.66x104
14a
2.23 x103
3.69 x102
2
1.63 x10
3.50 x101
0
6 x101
0
0
0
773
25
1.66x104
15
0
0
0
0
1.80 x10
7
10734
0
0
0
0
0
0
1.95 x103
2
1.67 x10
3.38 x104
1.80 x10
0
6 x101
0
0
0
773
25
4.67x104
15a
0
0
0
0
90
GROUP 1
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
Nickel Oxide
Nickel
Temperature (K)
Pressure (bar)
Total
0
0
0
0
0
1.07 x105
0
0
0
0
0
1.07 x105
0
0
0
0
0
0
2.1 x10
0
3
5.23 x10
0
0
0
771
2
1.12 x105
0
3
5.23 x10
0
0
0
298.01
1.9
1.12 x105
0
3
5.23 x10
0
0
0
298
1.9
5.23x103
0
0
0
0
0
298
1.9
1.07 x105
0
1
6.6 x10
0
0
0
771.4
24.995
4.15 x104
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO

0
0
0
0
0
0
0
0
0
0
0
0
4
4
3.03 x10
3.03 x10
3.03 x104
0
2
2
2
1.67 x10
1.67 x10
1.67 x10
0
1.07 x105 1.05 x104 1.05 x104 0
0
0
0
0
0
0
0
4
3.71 x10
2.07 x102
0
0
16a
0
0
0
0
0
0
0
4
3.71 x10
2.07 x102
0
0
16b
0
0
0
0
0
0
0
4
3.71 x10
2.07 x102
0
0
16c
0
0
0
0
0
0
0
4
3.71 x10
2.07 x102
0
0
2.1 x10
0
1
6.6 x10
0
0
0
298.01
24.97
4.15 x104
2.1 x10
0
1
6.6 x10
0
0
0
298.01
24.97
3.1 x104

17
18
19
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4
3.71 x10
0
0
2.07 x102
0
0
3
5.78 x10
0
0
0
0
0
Volume 1
0
0
0
0
0
1.05 x104
1.80 x101
1
1.00 x10
1
1.20 x10
3.05 x104
2
2.07 x10
0
2.1 x10
0
0
0
0
0
298
24.97
1.05x104
0
1
6.6 x10
0
0
0
296.53
25
3.39 x104
20
0
0
0
0
0
0
0
0
3.07 x104
0
0
1.80 x101
1
1.00 x10
1
1.20 x10
3.05 x104
2
2.07 x10
0
2.1 x10
0
1
6.6 x10
0
0
0
773.15
25
3.39 x104
21
0
0
0
0
0
0
0
0
3.07 x104
0
0
0
0
0
3.71 x104
2
2.07 x10
5.78 x103
0
0
0
3.71 x104
2
2.07 x10
5.78 x103
0
0
0
0
0
773
24.78
4.31 x104
0
0
0
0
0
298.01
24.68
4.31 x104
21a
0
0
0
0
0
0
0
0
3.07 x104
0
0
22
0
0
0
0
0
0
0
0
0
0
0
91
GROUP 1
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
Nickel Oxide
Nickel
Temperature (K)
Pressure (bar)
Total
0
0
0
0
0
298
25
3.73 x104
Component | Stream No. U1
Methane, CH4
0
Ethane, C2H6
0
Propane, C3H8
0
n-Butane, C4H10
0
i-Butane, C4H10
0
n-Pentane, C5H12
0
n-Hexane, C6H14
0
Carbon Dioxide, CO2 0
Nitrogen, N2
0
Water, H2O
0
Carbon Monoxide, CO 0
Hydrogen Sulphide,
H2S
0
Hydrogen , H2
0
Oxygen, O2
0
Nickel Oxide
0
Nickel
0
Temperature (K)
303
Pressure (bar)
33
Total
0

Volume 1
0
0
0
0
0
398
70
3.73 x104
U2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
298
70
3.73 x104
U3
0
0
0
0
0
0
0
0
0
3
4.83 x10
0
0
0
0
0
0
298
70
3.73 x104
U4
0
0
0
0
0
0
0
0
0
4
3.01 x10
0
0
0
0
0
0
317.55
150
3.73 x104
U5
3
2.05 x10
2
3.69 x10
1.63 x101
3.5 x101
1.8 x101
1
1 x10
1.2 x101
1.34 x102
4.1 x101
0
0
0
0
0
0
0
298
25
5.78x103
U6
3
2.05 x10
2
3.69 x10
1.63 x101
3.5 x101
1.8 x101
1
1 x10
1.2 x101
1.34 x102
4.1 x101
0
0
0
0
0
0
3.06 x104
773
25
3.06 x104
U7
0
0
0
0
0
0
0
0
3.07 x104
0
0
0
0
0
3.9 x104
0
773
25
6.96 x104
U8
0
0
0
0
0
0
0
0
3.07 x104
0
0
0
0
0
0
0
773
25
3.07 x104
U9
0
0
0
0
0
0
0
0
3.07 x104
0
0
0
0
0
0
0
298
24.9
3.07 x104
U10
0
0
0
0
0
0
0
0
0
5
1.07 x10
0
7 x10-2
0
0
0
0
303
32.83
7.00 x10-2
0
0
0
0
0
673
32.93
4.83 x103
0
0
0
0
0
773
25
3.01 x104
0
0
0
0
0
303
32.93
2.84 x103
0
0
0
0
0
287.75
25
2.84 x103
0
0
9.31 x103
0
0
283
1
4.00 x104
0
0
9.31 x103
0
0
849.8
25
4.00 x104
0
0
9.31 x103
0
0
773
25
4.00 x104
0
0
0
0
0
773
2
1.07 x105
0
0
0
3.9 x104
0
773
25
3.90 x104
92
GROUP 1

Volume 1
Energy Balance for individual streams (Design 1 Part 1 Hand calculated)

Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen , H2
Oxygen, O2
MEA
Phase
Total
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
1
-1
-1.32x10
-1.84x10-2
-3
-7.75 x10
-3
-1.70 x10
-8.43x10-4
-4
-4.96x10
-5.91x10-4
-3.30x10-4
-3
-1.26x10
0
0
-4.30x10-7
0
0
0
Vapor
-1.66x10-1
7a
1
1.53 x10
0
0
0
0
0
0
7.23x10-1
5.65x10-2
2.77 x101
1a
-1
-1.32x10
-1.84x10-2
-3
-7.75x10
-3
-1.70x10
-8.43x10-4
-4
-4.96x10
-5.91 x10-4
-3.30x10-4
-3
-1.26x10
0
0
-4.30x10-7
0
0
0
Vapor
-1.66x10-1
8
-1
3.90x10
0
0
0
0
0
0
3.21
6.07x10-2
1.95 x101
1b
-2
4.53x10
6.47x10-3
-3
2.75x10
-4
5.99x10
2.98x10-4
-4
1.75x10
2.09x10-4
1.13x10-4
-4
4.20x10
0
0
1.44x10-7
0
0
0
Vapor
5.74x10-2
8a
-1
1.01x10
0
0
0
0
0
0
1.02
2.12x10-2
6.17
2
-2
4.53x10
6.47x10-3
-3
2.75x10
-4
5.99x10
2.98x10-4
-4
1.75x10
2.09x10-4
1.13x10-4
-4
4.20x10
0
0
1.44x10-7
0
0
0
Vapor
5.74x10-2
9
-1
1.32x10
0
0
0
0
0
0
3.59
2.63x10-2
5.97
Energy of the stream (MW)

3
4
4a
-2
-2
3.46
4.53x10
2.94x10
-3
-3
6.47x10
4.19x10
5.70x10-1
-3
-3
-1
2.75x10
1.77x10
2.48x10
-4
-4
-2
5.99x10
3.92x10
5.35 x10
2.98x10-4 1.95x10-4 2.70 x10-2
-4
-4
-2
1.75x10
1.12x10
1.54 x10
2.09x10-4 1.33x10-4 1.83 x10-2
1.13x10-4 7.36x10-4 7.25 x10-2
-4
-4
-2
4.20x10
2.68x10
2.11 x10
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Vapor
Vapor
Vapor
5.74x10-2 3.72x10-4 4.49
9a
10
10a
-2
-2
-4
4.87x10
6.20x10
8.52x10
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1.49
2.46
3.81x10-2
1.17x10-2 1.43x10-2 2.68x10-4
2.60
2.72
4.90x10-2
5
3.46
5.70x10-1
-1
2.48x10
-2
5.35 x10
2.70 x10-2
-2
1.54 x10
1.83 x10-2
7.25 x10-2
-2
2.11 x10
1.16
0
0
0
0
0
Vapor
5.65
11
-4
8.52x10
0
0
0
0
0
0
3.81x10-2
2.68x10-4
0
5a
3.46
5.70x10-1
-1
2.48x10
-2
5.35 x10
2.70 x10-2
-2
1.54 x10
1.83 x10-2
7.25 x10-2
-2
2.11 x10
1.16E+06
0
0
0
0
0
Vapor
5.65
12
0
0
0
0
0
0
0
0
0
0
6
4.60
0
0
0
0
0
0
2.63x10-1
-2
2.20x10
9.21x10-1
-3
2.37x10
0
0
0
0
Vapor
5.91
13
-4
8.52x10
0
0
0
0
0
0
3.81x10-2
2.68x10-4
0
7
4.60
0
0
0
0
0
0
2.63x10-1
-2
2.20x10
9.96
-3
2.37x10
1.05x10-1
0
0
Vapor
14.9
14
-4
8.52x10
0
0
0
0
0
0
3.81x10-2
1.72x10-1
0
93
GROUP 1
Carbon Monoxide, CO
Hydrogen , H2
Oxygen, O2
Phase
MEA
Total
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen , H2
Oxygen, O2
MEA
Phase
Total
6.08x10-3
0
2.69x10-1
0
Vapor
0
1
4.4 x10
15
-3.10x10-2
-3
-4.14x10
-1.76x10-3
-3.77x10-4
-1.87x10-4
-1.15x10-4
-4
-1.37x10
-2
-7.15x10
-3.25x10-1
0
-3.24x10-3
0
-2.29x10-2
-8.66x10-2
0
Vapor
-5.47x10-1
5.34
0
2.13 x101
0
Vapor
0
1
4.99 x10
16
0
0
0
0
0
0
0
8.53
1.81 x101
5.89
0
0
0
4.69x10-1
Vapor
3.3 x101

1.87
8.91x10-1
3.95x10-1 9.21x10-2 1.71x10-3
0
0
0
0
0
1
7.2
4.76
6.14
1.02 x10
1.16x10-1
0
0
0
0
0
Vapor
Vapor
Vapor
Mixed
Vapor
0
0
0
0
0
1
1
1
-1
9.31
1.65 x10
2.09 x10
1.15 x10
2.06x10
U1
U2
U3
U4
U5
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1.16
9.04
0
0
4.90x10-2
0
0
0
0
0
-7
0
0
0
0
1.44x10
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Vapor
Vapor
Vapor
Vapor
Liquid
-7
1.16
9.04
0
1.44x10
4.90x10-2
Volume 1
1.71x10-3
0
1.16x10-1
0
Vapor
0
-1
1.57x10
U6
1.60x10-2
-3
2.27x10
9.75x10-4
2.07x10-4
1.03x10-4
6.35x10-5
-5
7.56x10
-4
3.89x10
1.52x10-4
0
0
0
0
0
0
Vapor
2.02x10-2
0
0
1.04x10-1
0
Vapor
0
-1
1.04x10
U6a
1.60x10-2
-3
2.27x10
9.75x10-4
2.07x10-4
1.03x10-4
6.35x10-5
-5
7.56x10
-4
3.89x10
1.52x10-4
0
0
0
0
0
0
Vapor
2.02x10-2
1.71x10-3
0
1.21x10-2
0
Vapor
0
-2
5.31x10
U7
0
0
0
0
0
0
0
0
-5.15x10-1
0
0
0
0
-1.37x10-1
0
Vapor
-6.52x10-1
1.71x10-3
0
1.21x10-2
-2
4.60x10
Vapor
0
-1
2.71x10
94
GROUP 1

Volume 1
Energy Balance for individual streams (Design 1 Part 2 Unisim)

Stream number
Phase
Total
Stream number
Phase
Total
Stream number
Phase
Total
Stream number
Phase
Total
16
Vapor
2
6.26 x10
22
Liquid
3
-2.67 x10
28
Vapor
9.66 x102
R1
Liquid
3
-2.52 x10
16a
Mixed
2
1.22 x10
23
Liquid
3
2.46 x10
28a
Mixed
-2.48 x103
R1a
Liquid
3
-2.52 x10
17
Vapor
2
2.03 x10
24
Liquid
2
1.21 x10
29
Vapor
1.66 x103
R2
Liquid
2
-1.32 x10
17a
Vapor
2
3.01 x10
24a
Liquid
1
4.13 x10
29a
Vapor
-1.63 x103
R3
Liquid
3
-2.65 x10

17b
18
19
Mixed
Vapor
Liquid
2
2
3
1.55 x10
1.91 x10
-2.640 x10
25
25a
25b
Liquid
Liquid
Liquid
3
3
3
-2.61 x10 -2.61 x10 -2.61 x10
29b
29c
29d
Vapor
Vapor
Vapor
-1.66 x103 -1.63 x103 -1.66 x103
U8
U9
Liquid
Liquid
1
1
-8.07 x10 -36.4 x10
19a
Liquid
3
-2.560 x10
25c
Liquid
3
-2.61 x10
29e
Vapor
-1.65 x103
20
Vapor
3
1.460 x10
26
2
2.1 x10
29f
Liquid
-1.71 x103
21
Liquid
3
-1.1 x10
26a
21a
Liquid
3
-1.1 x10
27
9.59
29g
Liquid
-1.71 x103
1.41 x10
30
Liquid
-1.7 x103
95
GROUP 1

Volume 1
Energy Balance for individual streams (Design 2)

Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide,
CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide,
CO
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
Nickel Oxide
Nickel
Phase
Total
1
-9.54x10-2
-1.33x10-2
-3
-5.58x10
-3
-1.26x10
-6.22x10-4
-3.35x10-4
-4
-3.99x10
1a
-9.54x10-2
-1.33x10-2
-3
-5.58x10
-3
-1.26x10
-6.22x10-4
-3.35x10-4
-4
-3.99x10
1b
3.28x10-2
4.68x10-3
-3
1.98x10
-4
4.42x10
2.20x10-4
1.18x10-4
-4
1.41x10
2
3.28x10-2
4.68x10-3
-3
1.98x10
-4
4.42x10
2.20x10-4
1.18x10-4
-4
1.41x10

3
4
4a
3.28x10-2
2.65x10-2 3.12
4.68x10-3
3.77x10-3 5.13x10-1
-3
-3
-1
1.98x10
1.59x10
2.23x10
-4
-4
-2
4.42x10
3.53x10
4.82x10
2.20x10-4
1.76x10-4 2.43x10-2
1.18x10-4
1.01x10-4 1.39x10-2
-4
-4
-2
1.41x10
1.20x10
1.65x10
-2.40x10-3
-2.40x10-3
8.20x10-4
8.20x10-4
8.20x10-4
-9.00x10
0
-3
-9.00x10
0
-3
0
-7
-3.11x10
0
0
0
0
Vapor
-1.20x10-1
Methane, CH4
5.43
Ethane, C2H6
0
Propane, C3H8
0
n-Butane, C4H10
0
3.00x10
0
-4
0
-7
-3.11x10
0
0
0
0
Vapor
-1.20x10-1
8
0
0
0
0
3.00x10
0
-4
0
-7
1.04x10
0
0
0
0
Vapor
4.15x10-2
8a
0
0
0
0
-7
1.04x10
0
0
0
0
Vapor
4.15x10-2
9
0
0
0
0
3.00x10
0
-4
6.63x10-4
2.41x10
0
-4
6.52x10-2
1.90x10
0
-2
5
3.12
5.13x10-1
-1
2.23x10
-2
4.82x10
2.43x10-2
1.39x10-2
-2
1.65x10
6
4.14
0
0
0
0
0
0
6a
3.92
0
0
0
0
0
0
6b
5.43
0
0
0
0
0
0
6.52x10-2
2.37x10-1
2.26x10-1
2.98x10-1
-2
1.98x10
8.29x10-1
-2
1.90x10
7.93x10-1
-2
2.46x10
1.04
-2
-3
2.04x10
-3
2.66x10
-3
1.90x10
1.04
2.14x10
0
0
0
0
0
Vapor
4.15x10-2
10
0
0
0
0
0
0
0
0
0
Vapor
3.35x10-2
11
-1
1.42x10
0
0
0
0
0
0
0
0
Vapor
4.04
11a
1.73
0
0
0
0
0
0
0
0
Vapor
5.08
12
1.73
0
0
0
0
9.45x10-2
0
0
0
Vapor
5.32
13
0
0
0
0
0
9.07x10-2
0
0
0
Vapor
5.05
14
-3
-2.11x10
-4
-2.63x10
-1.11x10-4
-5
-2.44x10
0
1.16x10-1
0
0
0
Vapor
6.90
14a
1.18
-1
1.71x10
7.45x10-2
-2
1.59x10
96
GROUP 1
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide,
CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide,
CO
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
Nickel Oxide
Nickel
Phase
Total
0
0
0

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2.46x10-2
9.51
0
0
1
3 x10
0
0
1
-6.55 x10
0
0
0
0
0
1
-6.55 x10
2.66x10-3
0
1.01 x101
0
0
0
Vapor
4.01 x101
15a
0
0
0
0
0
0
0
0
2.08x10-4
0
0
0
Mixed
-6.55 x101
16
0
0
0
0
0
0
0
0
0
0
0
0
Vapor
0
16a
0
0
0
0
0
0
0
2.98x10-1
0
1.16x10-1
0
0
0
Vapor
1.54 x101
Methane, CH4
0
Ethane, C2H6
0
Propane, C3H8
0
n-Butane, C4H10
0
i-Butane, C4H10
0
n-Pentane, C5H12 0
n-Hexane, C6H14 0
Carbon Dioxide,
5.68
CO2
-2
Nitrogen, N2
3.05x10
Water, H2O
1.62
Carbon Monoxide,
CO
0
Hydrogen Sulphide,
H2S
0
Hydrogen , H2
0
8.71x10-5
6.00x10
-2.97
-7
0
0
0
1.30
1.14x10
0
-2
Volume 1
0
0
0
0
0
0
-1.21x10-5
-7.03
-8.37
8.01x10-3
-3
4.63x10
5.49x10-3
4.62
7.11x10-5
7.11x10-5
-1.05x10-2
4.66
2.45x10-2
2.93
4.83x10-7
-5
5.43x10
4.83x10-7
0
0
-5.38
-8.82x10-5
0
3.05x10-2
0
3.12x10-2
-5.38
6.07x10-7
-8.92x10-5
3.14x10-2
0
0
0
0
0
Liquid
-6.55 x101
16b
0
0
0
0
0
0
0
0
1.27x10-1
0
0
0
Vapor
7.88
16c
0
0
0
0
0
0
0
0
2.62
0
0
0
Mixed
-5.38
17
0
0
0
0
0
0
0
0
2.62
0
0
0
Vapor
7.66x10-5
18
0
0
0
0
0
0
0
0
0
0
0
0
Liquid
-5.38
19
0
0
0
0
0
0
0
0
-3.85x10-4
0
0
0
Vapor
-1.36x10-2
20
0
0
0
0
0
0
0
0
1.27x10-1
0
0
0
Vapor
6.31
21
0
0
0
0
0
0
0
0
0
0
0
0
0
4.86x10-1
0
0
-2.97
0
0
0
0
4.52
0
0
4.52
0
4.26x10
0
-3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
97
GROUP 1
Oxygen, O2
Nickel Oxide
Nickel
Phase
Total
0
0
0
Vapor
7.33
Component | Stream No. 21a
Methane, CH4
0
Ethane, C2H6
0
Propane, C3H8
0
n-Butane, C4H10
0
i-Butane, C4H10
0
n-Pentane, C5H12 0
n-Hexane, C6H14 0
Carbon Dioxide,
CO2
0
Nitrogen, N2
0
Water, H2O
0
Carbon Monoxide,
CO
0
Hydrogen Sulphide,
H2S
0
Hydrogen , H2
0
Oxygen, O2
0
Nickel Oxide
0
Nickel
0
Phase
Vapor
Total
0

0
0
0
0
0
0
0
0
0
0
0
0
Vapor
Vapor
Vapor
Liquid
4.90x10-1
1.31
0
0
U2
U3
U4
U5
6.37x10-3
0
0
0
-4
9.08x10
0
0
0
-4
3.85x10
0
0
0
8.43x10-5
0
0
0
4.20x10-5
0
0
0
2.44x10-5
0
0
0
-5
2.90x10
0
0
0
0
0
0
Vapor
-2.97
22
0
0
0
0
0
0
0
0
0
0
Vapor
0
U1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1.04x10-7
0
0
8.47
0
0
0
2.94
0
Vapor
2.94
0
0
0
0
0
Vapor
0
1.04
0
0
0
0
Vapor
1.04
0
0
0
0
0
Vapor
1.04x10-7
0
0
0
0
0
Vapor
8.47
0
0
0
0
0
Vapor
8.06x10-3
1.58x10
-4
5.88x10
0
-5
Volume 1
0
0
0
Liquid
-2.97
U6
-1.27x10-2
-3
-1.79x10
-4
-7.53x10
-1.66x10-4
-8.23x10-5
-4.78x10-5
-5
-5.69x10
0
0
2.94
Vapor
2.94
U7
0
0
0
0
0
0
0
0
2.94
Vapor
7.46
U8
0
0
0
0
0
0
0
0
0
0
Vapor
4.52
U9
0
0
0
0
0
0
0
0
-1.33x10-1
0
0
5.3
0
0
4.52
0
0
0
0
0
0
Vapor
-1.61x10-2
0
0
-3.55x10-2
0
0
Vapor
-1.69x10-1
0
0
1.52
0
0
Vapor
6.86
0
0
1.29
0
0
Vapor
5.81
-3.19x10
-4
-1.20x10
0
-4
98
GROUP 1
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen , H2
Oxygen, O2
Nickel Oxide
Nickel
Phase
Total

Volume 1
U10
0
0
0
0
0
0
0
0
0
3.01 x101
0
0
0
0
0
0
Vapor
3.01 x101
99
GROUP 1

Volume 1
Appendix F: Process Selection

Table F-1: Process Selection Scoring and Explanation
Toxicity
Corrosiveness
0
Relatively
harmless
No evidence of
corrosiveness
1
Slightly toxic
2
Moderately toxic
3
Highly toxic
4
Extremely toxic
Corrosion of little
concern
Corrosion may be a
concern
Concern:
requires
special
materials
Suggestive
evidence of
carcinogenicity but
not sufficient to
assess
Combustible liquid
flash point of 100F
to 200F
Likely to be
carcinogenic
to humans
Special
materials and
process
alterations
required
Carcinogenic to
humans
Carcinogenicity
Not likely to be
carcinogenic to
humans
Data is
inadequate to
assess human
carcinogenicity
Flammability
Not
combustible
Combustible if
heated
Reactivity
Temperature
(deg C)
Pressure
(absolute value
- bar)
Minimal
Below 200
Slight
200-500
Atmospheric
Safety
Environmental
Maturity
Capital Cost
Economical
Operating Cost
Moderate
500-800
Flammable
liquid flash
point below
100F
Serious
800-1000
Flammable gas
or extremely
flammable
liquid
Severe
Above 1000
1-50
50-100
100-150
150 or greater
No effect on
environment
Possible small
disturbance to
local ecosystem
Toxic release
Hazard to
public health
and ecosystem
TRL=8-9
Cheapest
Cheapest
TRL=6-7
Cheap
Cheap
TRL=5-4
Moderate
Moderate
TRL=3-2
Expensive
Expensive
Long term
effect or need
for emergency
evacuation
TRL=1
Most expensive
Most expensive
Carcinogenic source - http://www.toxipedia.org/display/toxipedia/Hazard+Rankings
TRL Classification (Technology Readiness Levels for the DOE)

TRL 1: Scientific research begins applications to R&D. This is the lowest level of technology readiness.
TRL 3-2: Active R&D is initiated, with analytical studies. Practical applications can be invented.
TRL 5-4: Basic technology components are integrated with reasonably realistic supporting elements. Tested in a
simulated environment.
TRL 6-7: Prototype near or at planned operational system, demonstration in operational environment.
TRL 8-9: Technology proven to work. Completed and qualified, successful in operations.
100
GROUP 1

Table F-2: Scoring Matrix for Desulphurisation
Volume 1
Safety
Economical
Flammability
Reactivity
Temperature
Pressure
Environmental
Maturity
Capital Cost
Operating Cost
Dry based
0.57
3.57
Total
Carcinogenicity
AVERAGE
Corrosiveness
AVERAGE
Toxicity
Wet based
Table F-3: Scoring Matrix for Hydrogen Production

Safety
Economical
Flammability
Reactivity
Temperature
Pressure
Environmental
Maturity
Capital Cost
Operating Cost
1.28
2.5
4.78
CPOx
1.28
2.5
4.78
ATR
1.14
5.14
Total
Carcinogenicity
AVERAGE
Corrosiveness
AVERAGE
Toxicity
SMR
Table F-4: Scoring Matrix for Carbon Capture

Safety
Economical
Maturity
CAPEX
OPEX
AV
1.57
6.57
PSA
3.5
5.5
CL
Cryogenic
0.14
6.14
AV
Total
Environmental
Pressure
Temperature
Reactivity
Flammability
Carcinogenicity
Corrosiveness
Toxicity
Amine Absorption
Post-combustion and oxy-combustion
At SMR stage
SERP
1.43
7.43
Membranes
0.86
2.86
101
GROUP 1

Volume 1
Appendix G: Diagrams for process selection
Figure G-1: Block Flow Diagram of the Hydrogen Production Plant with identification of the streams containing
CO2[113]
Figure G-2: A typical Amine Absorption Process [114]
Figure G-3: Iron Oxide PFD

102
GROUP 1

Volume 1
Appendix H: Start-up times

Table H-1: Start up Sequence for Design 1
Start-up Sequence for Design 1
1. MEA Carbon Capture Unit
2. Carbon Compression Train
3. Furnace
4. Steam Methane Reformer
5. Pre-Reformer
6. Water Gas Shifts
7. Desulphurisation Unit
8. PSA Unit
Total Time Required for Start-Up:
Duration (hours)
8.5
2
10.5
13.5
6.5
3.5
0.5
0.5
22
Table H-2: Start-up Sequence for Design 2

Start-up Sequence for Design 2
1. SMR Membrane Reactor
2. Pre-Reformer
3. Air Reactor
4. Desulphurisation Unit
5. Fuel Reactor
Total Time Required for Start-Up:
Duration (hours)
10
6.5
0.5
0.5
1
10.5
103
GROUP 1

Volume 1
Universal assumptions:
1. Inspection and testing has already been conducted.
2. Heating and cooling water is already at specification.
3. Pumps are already primed.
Design 1 assumptions:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
MEA pressurisation time is 5 hours.

MEA heating and surge drum filling takes 3.3 hours.
CO2 compression chain takes 2 hours for its first run.
Sulfatreat start-up takes 30 minute, to account for the time take for the stream to flow through the beds.
Pre-reformer start up step takes 1 hour.
Pre-reformer reduction step takes 0.5 hours.
Rate of pressurisation for pre-reformer can be applied to WGS reactors.
SMR begins heating when the furnace begins heating.
SMR temperature takes 2 hours to reach steady state with the furnace.
SMR requires 1 hour to introduce feed.
WGS takes 1 hour for the stream composition to reach specification.
PSA start-up is complete after 1 cycle.
Design 2 assumptions:
1.
2.
3.
4.
5.
6.
7.
Sulfatreat start-up will take the same time as design 1.

Pre-reformer start-up will take the same time as design 1.
Membrane SMR heating rate of 50oC per hour is tolerated.
Ambient temperature is 30oC.
Fuel reactor start up takes 1 hour to complete.
Air reactor has undergone start-up after fluidisation has occurred.
SMR has reached required productivity after 0.5 hours.
Pre-reformer pressurisation time:

First volume equivalent at lower pressure was calculated:
=
2 8 = 30
= 120
Next the difference between this volume and the reactor volume was calculated:
=
= 120 8
= 112
Then time taken to fil this volume was calculated, the largest flowrate was used for this example:
=
= 112/60
= 1.867
This was rounded up to 2 hours.
104
GROUP 1

Volume 1
WGS pressurisation time:

First the pressurisation rate for the pre-reformer must be found, taking into account the volume:
28
=
(1.867 60) 8
=
= 0.03125.
From here the pressure difference in the WGS pressurisation stage was calculated:
=
= 30 1
= 29
These 2 values were then used to calculate the time required to pressurise the WGS reactors.
29
=
6 0.0135
= 154.7
=
This was converted to 2.58 hours for inclusion in the overall start-up table.
Heating of membrane SMR:
First the difference in temperature of the membrane SMR after heating and ambient temperature was calculated:
=
= 500 30
= 470
This difference in temperature, along with the heating rate for the membrane SMR reactor, was used to calculate
the time required to heat the reactor:
=
470
50
= 9.4
Table H-3: Nomenclature list for Appendix H
= 1 ()
= 2 ()
= 1 ( )
= 2 ( )
= ( )
= ()
= ( .
Nomenclature
= (. . )
= ()
= ( )
= 1 ( )
= 2 ( )
= ( . )
)
105

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Group Synergy:

Production of High Purity Hydrogen with CO 2

INTRODUCTION AND DESIGN ........................................................................................................................ 2

PROCESS SELECTION ..................................................................................................................................... 6

PROCESS FLOW DIAGRAM AND PROCESS DESCRIPTION ............................................................................... 15

PROCESS FLOW DIAGRAM FOR DESIGN 2 .................................................................................................... 20

ENERGY AND MATERIAL BALANCES ............................................................................................................. 23

Overall Mass Balance .............................................................................................................................. 24

THERMODYNAMICS AND CHEMISTRY ......................................................................................................... 26

HAZARDS AND SAFETY ................................................................................................................................ 34

ENVIRONMENTAL IMPACT .......................................................................................................................... 39

ECONOMIC ANALYSIS OF THE TWO DESIGNS ............................................................................................... 44

START UP AND SHUT DOWN ................................................................................................................... 49

RECOMMENDATIONS AND CONCLUSIONS ............................................................................................... 54

The University of Edinburgh School Of Engineering

The University of Edinburgh School Of Engineering

Introduction and Design

Carbon Dioxide Product

Discussion of Design Remit in a Chemical Engineering Context

The University of Edinburgh School Of Engineering

The University of Edinburgh School Of Engineering

The University of Edinburgh School Of Engineering

The University of Edinburgh School Of Engineering

The University of Edinburgh School Of Engineering

The University of Edinburgh School Of Engineering

The University of Edinburgh School Of Engineering

High level of maturity

Require external heat

Relatively new process

Thermally neutral system

Very precise control

Mainly used for smaller

Very limited information

Very limited information

The University of Edinburgh School Of Engineering

Figure 2-1: Process flow diagram for chemical absorption[42]

The University of Edinburgh School Of Engineering

The University of Edinburgh School Of Engineering

Figure 2-2: Process flow diagram of

The University of Edinburgh School Of Engineering

2.6.6 Cryogenic Capture

Figure 2-3: Process flow diagram of cryogenic CC[53]

High purity CO2

Low temperatures and

High SMR conversions

Removal of water additional step

Small flexibility in flue

Not mature enough

The University of Edinburgh School Of Engineering

The University of Edinburgh School Of Engineering

Process Flow Diagram and Process Description for Design 1

Figure 3-1: Process Flow Diagram for Design 1

The University of Edinburgh School Of Engineering

3.2.1 Process Description

The University of Edinburgh School Of Engineering

The University of Edinburgh School Of Engineering

The University of Edinburgh School Of Engineering

The University of Edinburgh School Of Engineering

Process Flow Diagram and Process Description for Design 2

Figure 4-1: Process Flow diagram for design 2

The University of Edinburgh School Of Engineering

4.2.1 Process Description

The University of Edinburgh School Of Engineering

Cooling of cyclone flue gas before release