DLMethionineCarbonateProcess

D,L-methionine production via the
carbonate process
The process
In the process shown in Figure 1, DLM is
obtained via the carbonate process from
3-methylthiopropionaldehyde (MMP) and
hydrogen cyanide (HCN), without forming coproducts. The process presented here is similar
to one developed by Evonik Industries AG (Essen, Germany; www.evonik.com), and can be
divided into four main areas: hydantoin production; hydantoin hydrolysis; DLM production and
filtration; and drying. Hydantoin corresponds
to the intermediate 5-(2-methylmercaptoethyl)hydantoin generated in the process.
Hydantoin production. MMP, HCN and an
aqueous solution of carbon dioxide (CO2) and
ammonia (NH3) are fed to the hydantoin primary reactor. A gas stream containing CO2, NH3
and impurities leaves the reactor and is washed
with MMP and water in a scrubbing column.
Purified CO2 is released in the overheads and
used in DLM production. The reaction mixture
is fed to a hydantoin secondary reactor, where
the reaction is completed.
Hydantoin hydrolysis. The hydantoin product
stream and potassium carbonate (K2CO3)
are fed to the hydrolysis reactive column,
which contains zirconium fittings that serve
as catalysts and prevent corrosion. CO2 and
NH3 are liberated in the overhead stream
of the column and recycled to the hydantoin
primary reactor. The bottom stream, containing potassium methioninate (KMET), is sent to
the DLM production portion of the process.
K2CO3 is obtained from the regeneration of a
80
150
90
400
300
580
ethionine is an essential amino acid

that is not synthesized by animals, so
it must be obtained from their diets.
Synthetic methionine is traditionally commercially available in two varieties: D,L-methionine
(DLM), a racemic mixture of the two stereoisomers, and methionine hydroxy analog (MHA).
For animal nutrition, the two are equivalent.
Globally, 98% of methionine produced is used
as an animal feed additive, especially in the
poultry market. Methionine is also used in
pharmaceuticals and cosmetics.
n Total current capacity (2014) = 1,360,000 ton/yr

n Total planned capacity (2016) = 240,000 ton/yr
FIGURE 2. Worldwide methionine production capacity
potassium bicarbonate (KHCO3) solution from

DLM filtration. This occurs in a decarbonator,
where CO2 is separated in the overheads and
directed to the DLM reactor.
DLM production and filtration. The KMET stream
and recycled CO2 are fed to the DLM reactor,
forming KHCO3 and DLM. The methionine is
fed to a vacuum crystallizer and the crystals are
vacuum-filtered. The resulting KHCO3-containing filtrate is sent to the decarbonator.
Drying. The methionine cake is directed to a
dryer, where water is evaporated and sent to a
wash column before being used in methionine
washing during filtration. Methionine product
(99 wt.%) is sent to packaging and storage.
Economic performance
An economic evaluation of the process was
conducted, assuming a 150,000 ton/yr methionine unit erected on the U.S. Gulf Coast and
integrated with nearby MMP and HCN facilities. The storage autonomy is equal to 30 days
of operation for methionine, aqueous NH3 and
liquefied CO2. The estimated capital investment is about $390 million, while operating
expenses are about $2,600 per ton of product.
Global perspective
In the past few years, methionine global
demand has increased at an average rate of
5%/yr, and is expected to increase further.
This expansion of methionine demand is driven
by rising meat consumption and, in particular, growth in global poultry, associated with
population growth and increased purchasing
power, mainly in developing countries. Also,
there has been consolidation in the agricultural
sector, leading to larger, more industrialized
farms with more efficient animal nutrition with
higher inclusion rates of amino acids.
In this context, Asian markets present strong
methionine demand, driving its manufacture
toward that region. This can be observed
through the methionine capacity expansion
planned in this area (Figure 2). n
Editors Note: The content for this column is supplied
by Intratec Solutions LLC (Houston; www.intratec.us)
and edited by Chemical Engineering. The analyses
and models presented are prepared on the basis of
publicly available and non-confidential information.
The content represents the opinions of Intratec
only. More information about the methodology for
preparing analysis can be found, along with terms
of use, at www.intratec.us/che.
CW
1 ) Hydantoin primary reactor

To
flare
CO2 make-up
PW
ST
MMP
MMP+
Impurities
3 ) Scrubbing column
4 ) Hydrolysis reactive column
10
5 ) Decarbonator
K2CO3
make-up
MMP
HCN
CO2 make-up
H2O
NH3 make-up
2 ) Hydantoin secondary reactor
6 ) DLM reactor
CW
ST
7 ) Vacuum crystallizer
8 ) Vacuum filter
CW
9 ) Dryer
9
1
FIGURE 1. D,L-methionine production via carbonate process
10) Vacumm wash column
Methionine to
packaging and storage
11) Cooling tower

12) Steam boiler
CW
11
ST
12
CW Cooling water
ST Steam
PW Process water
Extracting 1,3-Butadiene
from a C4 Stream
By Intratec Solutions
he organic compound 1,3-butadiene

is a petrochemical commodity used as
a raw material for the production of
rubbers and plastics, such as polybutadiene
rubber (PR), styrene butadiene rubber (SBR),
and acrylonitrile butadiene styrene (ABS).
These materials are mainly applied in the
manufacture of automotive parts, tires and
cables. Also, 1,3-butadiene is used as an
intermediate in the manufacture of several
chemicals, such as adiponitrile, the raw
material for nylon production.
1,3-Butadiene is generally recovered from
C4 streams that are generated as byproducts of ethylene manufacture by naphthabased steam cracking. These C4 mixtures
are composed mostly of butadiene and
butenes, with smaller amounts of butanes
and acetylenes. To obtain the 1,3-butadiene
product stream, it must be extracted from the
C4 mixture. This can be accomplished using
several technologies, such as separation by
solvent extraction.
The process
The process depicted in Figure 1 is similar
to BASFs (Ludwigshafen, Germany; www.
basf.com) process for butadiene extraction using aqueous N-methylpyrrolidinone
(NMP) as a solvent.
Extractive distillation. The C4 mixture
containing butadiene, butenes, butanes
and acetylenes is fed to the first extractive column, where recycled NMP solvent
is added to the top section. The column
overhead stream, which consists of butanes
and butenes (raffinate-1), is sent to storage.
The bottom stream, containing butadiene,
acetylenes and some butenes absorbed in
NMP, is fed to the top of the rectifier column. In this column, remaining butenes are
separated in the top stream and recycled
to the first extractive column, while the
bottoms stream, containing mainly NMP,
is sent to the degassing section. Butadiene
and some acetylenes are separated as a
FIGURE 2.
BASFs NMP process plants around
the world. Each
mark in the map
corresponds to an
existing facility
side stream of the rectifier column, which

is fed to the second extractive column.
There, recycled NMP solvent is added to
the top to absorb the acetylenes, which
are recovered in the bottoms and returned
to the rectifier column. Crude butadiene is
recovered in the overheads and sent to the
butadiene-purification section.
Butadiene purification. In this section, the
crude butadiene stream is fed to the propyne column, where propyne is separated
in the overheads. The bottoms stream of
this column is sent to the butadiene distillation column, where 1,3-butadiene product
is obtained in the overhead stream and
heavy ends are separated in the bottoms.
Degassing. The NMP solvent from the
bottoms of the rectifier column is stripped
from the heavy hydrocarbons, which are
separated as the distillate stream of the
degassing column. These heavy hydrocarbons are then sent to a cooling column,
where they are cooled by direct contact
with NMP solvent and fed to the rectifier
column through a gas compressor. In the
degassing column, the acetylenes are
separated as a side stream and washed in
a scrubber before being purged. The NMP
recovered in the bottom stream is recycled
to the extractive distillation columns.
Propyne
Raffinate-1
An economic evaluation of the process
was conducted, taking into consideration
a unit processing a C4 stream to produce 100,000 ton/yr of 1,3-butadiene
erected on the U.S. Gulf Coast (the process
equipment is represented in the simplified
flowsheet below). The estimated total fixed
investment for the construction of this plant is
about $50 million.
An important feature of the presented
technology is its low susceptibility to impurities, rendering it adequate to process any
C4 stream, regardless of the butadiene
content. Also, plants using this technology
have been shown to operate continuously
for more than four years.
In addition, the BASF NMP process technology is currently applied in several plants
worldwide, as shown in Figure 2. n
Editors Note: The content for this column is
supplied by Intratec Solutions LLC (Houston; www.
intratec.us) and edited by Chemical Engineering.
The analyses and models presented herein are
prepared on the basis of publicly available and
non-confidential information. The information and
analysis are the opinions of Intratec and do not
represent the point of view of any third parties.
More information about the methodology for
preparing this type of analysis can be found,
along with terms of use, at www.intratec.us/che.
1,3-Butadiene product
1. First extractive column
CW
CW
2. Rectifier column
CW
3. Second extractive
column
4. Propyne column
CW
1
C4
mixture
Acetylenes
CW
ST
ST
Heavy
ends
5. Butadiene distillation
column
6. Gas compressor
8
7
7. Cooling column
8. Degassing column
9. Scrubber
ST
ST
CW
FIGURE 1. This 1,3-butadiene extraction process is similar to BASFs NMP process
CW Cooling water
ST Steam
1,4-Butanediol from
Bio-Succinic Acid
1,4-Butanediol unit
Bio-succinic acid unit
Biomass source unit
he compound 1,4-butanediol (BDO) is a
Milling,
versatile intermediate
Lights
Hydrogen
Sugarcane
treatment and
Biofor the chemical industry. Its
sugar inversion
succinic
largest derivative product is
acid
Cell separation,
Hydrogenation
tetrahydrofuran (THF), which
BDO
Purification
or
Glucose Fermentation
recovery and
reaction
is used to make spandex
purification
fibers, resins, solvents and
printing inks. The second largMilling and
Corn
Water
saccharification
est product is polybutylene
Heavies
terephthalate (PBT), which
is used to make high-perforFIGURE 2. It is possible to integrate 1,4-butanediol and bio-succinic-acid production units
mance materials, electronics
The estimated capital investment (including
are reported in literature). Side products include
and automotive equipment.
total fixed investment, working capital and
THF, gamma-butyrolactone (GBL), and linear
BDO can be produced from different techother capital expenses) to build a plant would
alcohols (n-butanol, n-propanol). The amount
nologies and raw materials. The conventional
be $100 million in the U.S. Gulf Coast region
of each product depends on the catalyst and
method for manufacturing BDO is the Reppe
and $140 million in Brazil.
operational conditions used.
process, starting from acetylene. Other proThe bio-succinic acid is totally reacted,
cesses use propylene oxide, maleic anhydride,
Process perspective
and the unreacted hydrogen is compressed
1,3-butadiene or n-butane as starting points.
and recycled back to the reactor. The product
It may be an interesting consideration to
The newest technologies being developed for
stream is cooled and sent to flash vessels to
control the entire supply chain through the
BDO are bio-based pathways, which mostly
recover unreacted hydrogen and eliminate
integration of a bio-succinic-acid production
rely on bio-based succinic acid derived from
volatile materials.
unit with a BDO unit (see Figure 2). Also, the
biomass or a sugar substrate.
bio-BDO produced must include a premium
Succinic acid is a platform chemical that can Purification. The product from the flash vessels
is sent to a series of distillation columns to
price over its petrochemical counterpart. Both
be used to produce many products. However,
separate BDO from side products. In the first
measures are important to make the venture
its high cost of production from petroleum raw
column, BDO, GBL and water are removed
economically feasible.
sources limits its use to specific applications
from the bottoms and then sent to the drying
In addition, it is also an important research(such as pharmaceuticals and food additives).
column, where most of the water is removed.
and-development goal to find hydrogenation
According to the U.S. Dept. of Energy (DOE),
The columns top fraction is sent to a lights
catalysts that have the following qualities:
bio-succinic acid is a renewable building-block
column, to recover side-products as fuel.
Improved tolerance to impurities generated in
chemical with great potential for the future.
The recovered water is sent to a tank for furthe fermentation process (that produces biother disposal or to be recycled to an integrated
succinic acid). This can help reduce the costs
The process
bio-succinic acid production unit (see Figure
of bio-succinic acid purification
The process depicted in Figure 1 was compiled
2). The drying columns bottoms are sent to a
Increased selectivity of bio-succinic acid to
based on a U.S. patent published by BioAmber
BDO recovery column and further to a heavies
BDO, reducing the formation of side products
Inc. (Montreal, Canada; www.bio-amber.com;
column, where a stream of 99.5 wt.% BDO is
and the costs with BDO purification
U.S. patent no. 2011/0245515). The patent
finally achieved.
Both achievements can reduce investment and
discloses details about the initial reaction,
production costs. n
while the separation process was conceived by
Intratec and is based on well-known practices.
Hydrogenation reaction. A solution of biosupplied by Intratec Solutions LLC (Houston; www.
conducted based on data from the fourth quarsuccinic acid in water is pre-heated and sent to
ter of 2013. The following assumptions were
the fixed-bed hydrogenation reactor. Hydrogen
taken into consideration.
is compressed and also fed in excess to the
A 55,000-ton/yr BDO production unit (the
reactor. The process uses a bimetallic catalyst
process equipment is represented in Figure 1)
consisting of metals (including ruthenium, rherepresent the point of view of any third parties.
Storage capacity equal to 20 days of operanium, tin and others) on a carbon support.
tion for BDO and no storage for bio-succinic
The exothermic reaction product is mostly
preparing this type of analysis can be found, along
acid
BDO (selectivities to BDO of more than 90%
with terms of use, at www.intratec.us/che.
Offgas
Hydrogen
CW
1 ) Hydrogenation reactor
Lights
as fuel
ST
CW
2
Bio-succinic acid in water
CW
ST
Water for
disposal or
recycle
CW
CW
CW
8 ) Heavies column
BDO
5 ) Light-ends column
6 ) Drying column
7 ) BDO recovery column
CW
3
10
3 ) Low-pressure vessel
4 ) High-pressure column
CW
ST
2 ) High-pressure vessel
9 ) Cooling tower
10) Boiler
CW Cooling water
ST
ST
ST
ST
ST Steam
Heavies
FIGURE 1. The 1,4-butanediol process from bio-succinic acid that is shown here
is based on patent disclosures from BioAmber and well-known practices
A solution-based
route to LLDPE
olyethylene (PE) is the worlds largestvolume commodity polymer. Along with

high-density (HDPE) and low-density
(LDPE) polyethylene, linear low-density polyethylene (LLDPE) is one of the three main types
of PE. The global market for LLDPE is over 20
million metric tons per year, corresponding to
about 30% of the total PE produced.
In LLDPE production, three major types of
low-pressure technologies are used: slurry,
solution and gas-phase processes.
FIGURE 2.
Each mark on the map
corresponds to an
existing SclairTech
LLDPE plant. The
nominal capacity
of each plant follows
the legend below
The process
LLDPE is produced by copolymerization of
ethylene with alpha-olefins using Ziegler-Natta
catalysts. The most common co-monomers used
in LLDPE production are 1-butene, 1-hexene
and 1-octene.
Figure 1 illustrates the process for butenebased LLDPE production via a solution technology similar to Nova Chemicals (Calgary,
Alta.; www.novachem.com) solution-phase
technology, known as SclairTech (Figure 2).
The process shown is a swing process, which
is also capable of producing different LLDPE
and HDPE grades by utilizing other alphaolefins as co-monomers.
The process can be divided into four main
operation areas: purification and catalyst preparation; reaction; distillation; and finishing.
Purification and catalyst preparation. The cyclohexane solvent, ethylene and comonomers are
sent to fixed-bed adsorption systems to remove
water, oxygen and other polar impurities. The
catalysts used in the process are based on
mixtures of titanium and vanadium compounds,
in conjunction with aluminum alkyls cocatalysts.
These components are mixed with solvent and
pumped to the polymerization reactor.
Reaction. Ethylene and 1-butene comonomer
(in case of butene-based LLDPE) are dissolved
in cyclohexane solvent and sent to the reaction
step. The polymerization is carried out in a
solution phase, at a temperature above the
melting point of the resulting polymer. The reaction system consists of a tubular reactor and a
continuous-stirred-tank reactor (CSTR). The low
residence time of the reactors enables a high
flexibility for grade transitions, as well as verButene
Up to 149,000 ton/yr
From 250,000 to 349,000 ton/yr
From 150,000 to 249,000 ton/yr
At least 350,000 ton/yr
satility for the production of resins with a wide

range of densities, melt indexes and molecular
weight distributions. The reactor output stream
is fed into separator vessels, where unreacted
ethylene and co-monomers, solvent and any
other volatile matter are separated from the PE.
The polymer is sent to the finishing section while
the light stream moves to the distillation system.
Distillation. The distillation step comprises
five distillation columns in charge of recovering the unreacted ethylene and co-monomers;
recovering the solvent; purging impurities,
such as oligomers (also called grease), catalyst
and deactivators residues; and avoiding the
buildup of inert components, such as isomers
of the co-monomer.
Finishing. The resulting polymer from the reaction area is fed into an extruder, which is used
to incorporate the required additives, and to
pelletize the polymer. The product is then sent
to the product blending and storage stage.
Storage of products is equal to 20 days

of operation, and there is no storage for
feedstock
Outside battery limits (OSBL) units considered: steam boilers, cooling towers,
propylene refrigeration system, heat-transfer
fluid unit, control room and administrative
buildings
other capital expenses) to build the LLDPE plant
is about $220 million, and the operating cost
for butene-based LLDPE production is about
$1,220/ton.
The swing process depicted here allows
manufacturers to participate in major PE
market segments by producing both LLDPE and
HDPE resins. Thus, the producers can select the
best product mix, aimed at premium markets
with higher margins.
Edited by Scott Jenkins
An economic evaluation of the solution-phase
LLDPE process was conducted based on data
from the fourth quarter of 2012. The following
assumptions were taken into consideration:
A 350,000 ton/yr unit erected on the U.S.
Gulf Coast (the process equipment is represented in the simplified flowsheet)

and models presented herein are prepared on the basis of publicly available and non-confidential information. The information and analysis are the opinions of
Intratec and do not represent the point of view of any
third parties. More information about the methodology for preparing this type of analysis can be found,
Ethylene
to Fuel
RF
CW
Cyclohexane
1. Adsorption system
2. Tubular reactor
3. CSTR polymerization
reactor
4. Separators
5. Extruder and pelletizing
6. Low boiler column
7. Ethylene column
8. Comonomer column
9. Solvent column
10. Grease column
11. Refrigeration unit
12. Heat transfer fluid unit
13. Cooling tower
14. Boiler
BFW
ST
BFW
CW 6
ST
CW
4
9
HF
HF
ST
CW
CW
Additives
3
5
ST
ST
to Fuel
LLDPE
Catalyst and
cocatalyst
10
Deactivator
HF
to Fuel
FIGURE 1. Solution-phase LLDPE production process similar to Nova Chemicals SclairTech
RF
11 CW
13
HF
12
ST
14
HF
CW
RF
ST
BFW
Heat transfer fluid

Cooling water
Refrigeration fluid
Steam
Boiler feed water
Bio-based adipic acid

dipic acid is a dicarboxylic acid that

is widely applied to the production
of nylon, polyurethanes, plasticizers
and other polymers. Its main use is as one
of the raw materials for the manufacture of
the polyamide nylon 6,6. In 2012, 80% of
the total adipic-acid demand was directed
to this application.
The traditional production method for
adipic acid is based on the oxidation of
cyclohexane, a petroleum-based feedstock.
However, adipic acid is among the growing
group of industrial compounds for which
more-sustainable production methods have
been developed. A bio-based route to
adipic acid has emerged as an alternative
to petroleum-derived adipic acid. Bio-adipic
acid can be produced from renewable feedstocks, such as sugar and plant-based oils.
The process
Adipic acid is produced by a microorganism-based fermentation process that uses a
sucrose solution as the feedstock (Figure 1).
The process described below was compiled
based on information available in the published literature.
Sugar inversion. Sucrose is hydrolyzed to
fructose and glucose, which are the compounds actually consumed in fermentation.
The reaction occurs in an acidic medium,
obtained by adding HCl. After inversion,
the pH is adjusted with Na2CO3, and the
resulting stream is cooled before being sent
to the fermentation stage.
Fermentation. The sugars are converted to
adipic acid through an aerobic fermentation.
The microorganism culture is prepared for
inoculation in a two-stage seed train. An ammonia (NH3) solution from the recovery area
is added to the fermenters to maintain a pH
of about 7. The adipic acid produced in
the fermentation step reacts with ammonium
hydroxide, forming diammonium adipate.
Cell separation. The fermentation broth is

sent to agitation tanks and centrifuges in
order to completely remove cell biomass.
Ultrafiltration is used to remove remaining contaminants, such as cell debris and
precipitated proteins. The aqueous solution,
now free of microorganisms, is then sent to
the product-recovery area.
Product recovery. The solution is sent to the
concentration column, where diammonium
adipate is split into free ammonia and
adipic acid. The overhead stream, which
contains mostly ammonia and water, is sent
to the ammonia-recovery column and, afterwards, is recycled to the fermentation step.
The bottoms product stream contains dissolved adipic acid that is crystallized at low
temperatures. The slurry from the crystallizer
is centrifuged, and part of the mother liquor
is recycled to the concentration column. The
solid adipic acid product is dried and sent
to storage.
Water make-up
Fixed costs
FIGURE 2. Raw materials costs account for the
half of the operating expenses for a bio-based
adipic acid unit
stock, the bio-based process can be a good

alternative when compared to petroleumbased process for adipic acid production.
Research activity to achieve higher product
yield and selectivity may eventually lead
to the bio-based process becoming more
cost-effective than the conventional petroleumbased process.
Aside from the possible economic advantages, the production of bio-based adipic
acid can have an impact on environmental
issues. The bio-based process is more environmentally friendly and leads to an overall
reduction in oxides of nitrogen (NOx) and
other greenhouse-gas emissions compared
to what is normally produced during the
petroleum-based adipic acid process. n
NH3 make-up
1.
2.
3.
4.
5.
6.
7.
CW
8
To waste
treatment
Na2CO3
CW
Air
Net raw materials cost

Main utilities consumption
CW
HCl
28%

Microorganisms
seed
1
50%
An economic evaluation of the bio-based
adipic acid production process was conducted. The following assumptions were
taken into consideration:
A 83,000-ton/yr capacity plant erected
on the U.S. Gulf Coast
Storage of product is equal to 30 days
feedstock
Outside battery limits (OSBL) units considered: ammonia refrigeration system,
cooling towers and steam boilers
other capital expenses) for the construction
of such a plant amounts to about $340
million, and the operating cost is about
$2,150 per ton of product, as depicted in
Figure 2.
Due to the availability of low-cost feed-
Exhaust
gases
Sucrose
Solution
22%
7
8.
ST
To waste
treatment
ST
3
10
CW
CW
RF
Adipic
acid
12.
13.
9
RF
9.
10.
11.
11 CW
12
ST
13
To waste
treatment
FIGURE 1. Bio-based adipic acid production is based on fermentation, ultrailtration and crystallization processes
Hydrolysis reactor
Neutralization vessel
Air compressors
Seed trains
Fermenter
Cells centrifuge
Concentration
column
Ammonia recovery
column
Crystallizer
Dryer
NH3 refrigeration
unit
Cooling tower
Steam boiler
RF Refrigeration fluid
CW Cooling water
ST Steam
Production of Bio-based
Succinic Acid
The process
In the process depicted in Figure 1, succinic
acid is obtained via microbial fermentation of glucose from sugarcane juice. The
process steps and equipment were compiled
based on publically available information
from the scientific literature.
Sugar inversion. The sugar consumed in this
fermentation-based process is glucose. It is
obtained by the inversion of sucrose through
its hydrolysis to glucose and fructose. This is
achieved by subjecting the juice containing
sucrose to an acidic medium by addition
of hydrochloric acid (HCl). After inversion,
the pH is adjusted with sodium carbonate
(Na2CO3) and the stream is cooled before
being sent to the fermentation step.
Fermentation. Glucose is converted to
succinic acid through an anaerobic fermentation supplied with carbon dioxide.
The microorganism culture is prepared
for inoculation in a two-stage seed train.
Carbon dioxide is compressed, filtered and
Na2CO3
An economic evaluation of the bio-based
succinic acid process was conducted. The
following assumptions were taken into
consideration:
Gulf Coast (the process equipment is represented in the simplified flowsheet below)
Storage of product is equal to 30 days
feedstock
Outside battery limits (OSBL) units considered: steam boilers, cooling towers and
ammonium refrigeration system
other capital expenses) is about $260 mil-
2,500
2,000
1,500
1,000
500
0
Net raw materials costs
Main utilities consumptions
Fixed costs
FIGURE 2. The operating expenses for biosuccinic acid are broken down here
lion, and the operating expenses are about

$2,200/ton of product (Figure 2).
Beginning with high-value applications, bio-succinic acid has the potential to
become a key building block for commodity chemicals, since consumers of end-use
products are increasingly demanding more
eco-friendly products. Also, further development in bio-based succinic acid processes
will likely lead to more cost-effective production, resulting in an increase in the demand
for this product compared to the costly
petroleum-based succinic acid.
Based on these features, several new
projects for producing bio-based succinic
acid have begun operations, and others
are planned in the near future, thus growing the worldwide production capacity for
this key industry chemical. n
Editors Note: The content for this column is supplied by
Intratec Solutions LLC (Houston; www.intratec.us) and
edited by Chemical Engineering. The analyses and
models presented herein are prepared on the basis
of publicly available and non-confidential information.
The information and analysis are the opinions of Intratec and do not represent the point of view of any
third parties. More information about the methodology
for preparing this type of analysis can be found, along
Lights
Exhaust
gases
Cane
juice
HCl
cooled before being fed into the fermenter.

A solution of ammonia (NH3) is added to
the fermenters to maintain a pH level of
about 7.
Cell separation. The fermentation broth is
sent to surge tanks and then to centrifuges
in order to completely remove cell biomass.
Ultrafiltration is used to remove the remaining
contaminants, such as cell debris and precipitated proteins. Following that, the aqueous
solution, free of microorganisms, is sent to
the product recovery and purification area.
Recovery and purification. In this stage, a
decolorization process is performed with
the addition of activated carbon. Then, the
mixture is filtered to separate the activated
carbon. The aqueous phase is sent to a
vacuum-distillation column, where volatile
byproducts and some water are removed.
This distillation leads to a more concentrated succinic acid stream. The succinic
acid product is then crystallized at low
temperature. HCl is used to adjust pH,
allowing selective crystallization of succinic
acid. Succinic acid crystals are washed with
water in a filter and dried with hot air. Part
of the succinic acid product that is lost in the
filtrate is recycled to the distillation column.
$/ton of product
uccinic acid is an important industrial

chemical that is traditionally derived
from petroleum feedstocks. It can be
used in several areas from high-value
niche applications, such as food, beverages and pharmaceuticals, to large-volume
applications, such as plasticizers, resins and
coatings. However, the current market for
succinic acid is limited to specialized areas
because of its costly production process.
Bio-based succinic acid, produced from
renewable feedstocks, appears to be an alternative to the petroleum-derived chemical
and may have advantages surrounding concerns about rising atmospheric greenhouse
gas (GHG) concentrations and volatile
crude oil prices. Bio-succinic acid is chemically equivalent to conventionally produced
succinic acid, and is suitable for the same
applications. For more on bio-based succinic acid, see Chem. Eng., August 2013,
pp. 1417.
Activated
carbon
CW
Microorganisms
seed
1
Water
4
NH3
77
6
To waste
treatment
CW
CO2
ST
Purge
3
CW
CW
9
Succinic
acid
To waste
treatment
FIGURE 1. Bio-succinic acid is produced via the fermentation of glucose
RF
Process
water
Hot air
RF
HCl
8
10 CW
11
ST
12
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
Hydrolysis reactor
Neutralization vessel
CO2 compressors
Seed train
Fermenters
Cells centrifuge
Vacuum column
Crystallizer
Dryer
NH3 refrigeration unit
Cooling tower
Steam boiler
CW Cooling water
ST Steam
Producing Ethanol from

Lignocellulosic Biomass
ressing global issues, such as climate

change and declining energy security,
have led to an increasing interest in
the use of renewable feedstocks for fuel production. These feedstocks include lignocellulosic materials, such as waste biomass from
the agriculture and forest industries.
Ethanol is commonly produced by
fermentation of sugars from agricultural
feedstock mostly corn and sugarcane.
Several processes to produce ethanol by
fermenting lignocellulosic materials have
been developed. Two such processes have
been introduced by American Process Inc.
(Atlanta, Ga.; www.americanprocess.com),
one of which was covered in this column
last year (Chem. Eng., November 2013, p.
26). The other cellulosic ethanol process is
discussed below.
The process
The process for cellulosic ethanol production
depicted in Figure 1 is similar to the AVAP
process described in the World Intellectual
Property Organization (Geneva, Switzerland; www.wipo.int) patent published
by American Process Inc. (W.O. Patent
2011/044378A1).
Pretreatment. The biomass is heated with
a solution of SO2, ethanol and water and
then fractionated into its three lignocellulosic
components: hemicellulose, cellulose and
lignin. Hemicellulose and lignin are partially
dissolved, while cellulose remains insoluble.
Cellulose is washed and the filtrate is sent to
the stripping column, where SO2 and ethanol are recovered in the overhead stream,
which is condensed in an evaporator and
sent to a make-up vessel. The column bottoms material is concentrated in the evaporator, generating vapor that is compressed
and used as steam supply for the evaporator and for the columns reboiler.
Cellulose hydrolysis and fermentation. Cellulose is hydrolyzed into glucose monomers
FIGURE 2.
by an enzymatic reaction.
Wood
Wood fractionInsoluble lignin is separated
ation for the
and conducted to the hemimanufacture of
AVAP process (biomass fractionation)
cellulose hydrolysis area
different inal
and glucose is fermented to
products
ethanol. The broth is centrifuged, then the cells are
Cellulose
Hemicellulose
Lignin
treated with sulfuric acid and
recycled to the fermenters.
Hemicellulose hydrolysis
Pulp and paper
Ethanol
Energy
and fermentation. The
products
concentrated stream from the
pretreatment area is mixed
with the lignin from the enzymatic hydrolysis Economic performance
and pumped to the auto-hydrolysis reactor,
conducted, taking the following assumptions
where hemicellulose is hydrolyzed to monointo consideration:
mer sugars, such as xylose. The hydrolyzate
A biomass processing unit producing 58
is neutralized with lime to precipitate the
million gallons of anhydrous ethanol per
soluble lignin. Insoluble lignin is separated
year, built on the U.S. Gulf Coast
and burned to generate steam and energy
Storage of products is equal to 30 days
to supply plant demands. The monomer
sugars are fermented to ethanol.
feedstock
Distillation. The broths from the fermentaThe estimated capital expenses (including
tion steps are mixed and conducted to the
concentration column, where a vapor side
other expenses) for the construction of this
stream with 50% ethanol is obtained. The
plant are about $700 million.
bottoms material from this column is used to
An interesting application to the prewash cellulose. The side stream is fed to the
sented technology is its integration with
rectifying column, generating an overhead
the pulp-and-paper industry. In this case,
stream containing about 93% ethanol. The
the process can fractionate wood into its
ethanol product stream undergoes dehydraprimary components (cellulose, hemiceltion in a molecular sieve unit, leading to
lulose and lignin). Then, each fraction can
ethanol product with 99.5% purity.
be used in different applications, targeting
each toward the most profitable market
Key research features
(Figure 2). n
Regarding its process, American Process
says the following:
The application of enzymes only for celEditors Note: The content for this column is supplied
lulose hydrolysis requires a lower dose
of enzymes when compared to processes
and models presented herein are prepared on the baconverting both cellulose and hemicellusis of publicly available and non-confidential informalose by enzymatic hydrolysis
tion. The information and analysis are the opinions of
The process offers an energy-eficient
third parties. More information about the methodolrecovery of cooking chemicals, resulting in
ogy for preparing this type of analysis can be found,
low expenses with chemical make-up
1. Cooking digester
Enzyme
Vent
gases
Vent
gases
2. Cellulose washers
3. Stripping column
CW
Biomass
4. Make-up vessel
5. Two-effect evaporator
7
6
CW
6. Enzymatic hydrolysis reactor
CW
11
13
7. Cellulose fermenters
SO2
H2O
8. Auto-hydrolysis reactor
4
Sulfuric acid
Ethanol
Lime
ST
To waste
treatment
Recovered chemicals condensate
Electricity
10
Lignin
9. Neutralization vessel
10. Hemicelluloses fermenters
11. Concentration column
ST
9
ST
To waste
treatment
Ethanol
Vent
gases
8
5
12
CW
15
To waste
treatment
12. Rectifying column

13. Molecular sieve unit
14. Cooling tower
14
CW
15. Energy cogeneration unit

CW Cooling water
ST Steam
FIGURE 1. Cellulosic ethanol production process similar to the AVAP process from American Process Inc.
Ethanol from Sugarcane

The process
Ethanol from sugarcane is traditionally
produced by yeast fermentation of sugarcane
molasses. Commonly, raw sugar is obtained
as a co-product, through crystallization of
sugarcane raw juice. The major process steps
in sugarcane ethanol production (Figure 1) are
as follows:
Milling. Sugarcane is delivered from the field
to the factory, where it is weighed, cut and
shredded before being conducted to the mills,
where the raw cane juice is extracted. Sugarcane bagasse is obtained as a residue, and it
is burned to generate steam and electricity to
supply process demands.
Juice treatment. The raw cane juice is clarified
by treatment with phosphate and lime leading
to mud formation, which is separated in a
clarifier. The clarified juice is then concentrated
under vacuum in a multiple-effect evaporator,
forming a sugar syrup.
Sugar crystallization. Sugar crystallization
is accomplished in two vacuum calandrias,
where water is evaporated from the syrup
and crystallization is induced by the addition of a seeding solution. This process forms
a massecuite, a mixture of liquor and sugar
crystals. Next, crystallization is completed by
cooling in a crystallizer. The raw sugar is cen-
800
trifuged, dried and sent to storage.
In a third calandria-crystallizer set,
700
a massecuite is formed that will become the seeding solution to be used
600
at crystallization, and also the molasses for subsequent fermentation.
500
Fermentation. The sugars contained
in the molasses are fermented to
400
ethanol by yeast. Gases released
from the fermentation are washed
300
with recycle water in a gas-washing
column. The final broth is centri200
fuged, and the yeast cells are treated
with sulfuric acid and recycled to
100
the first fermenter. Meanwhile, the
ethanol-containing wine is sent to a
0
distillation apparatus.
Total fixed investment
Other capital expenses
Distillation. The ethanol solution is
Working capital
heated and fed to the concentration
column. The overhead of this column FIGURE 2. Capital expentitures for a sugarcane ethanol
is sent to the gas-washing column
plant erected in Brazil
and the vapor-side product stream,
containing about 50% ethanol, is fed
The electricity surplus generated in the plant
to a rectifying column that generates a 90%
is sold to the electric grid
ethanol vapor stream and recycle water, which
The estimated capital investment (including togoes to the gas-washing column. The ethanol
tal fixed investment, working capital and other
product stream undergoes dehydration in a
capital expenses) is about $670 million.
molecular sieve unit, leading to a product that
The process reported here allows sugis 99.5% pure ethanol.
arcane ethanol manufacturers to balance
ethanol and sugar production yields accordEconomic performance
ing to demand, rendering the activity flexible
to market fluctuations.
conducted based on data from the fourth quarBrazil is the main sugarcane ethanol producer
ter of 2012 (Figure 2). The following assumpand experienced, in the rst semester of 2013,
tions were taken into consideration:
a 7% increase in fuel ethanol consumption when
A 6 million-ton/yr sugarcane processing
compared to the same period of 2012.
unit producing 270 million L of anhydrous
ethanol and 420,000 ton of raw sugar per
year built in Brazil (the process equipment
is represented in the simplified flowsheet
below in Figure 1)
and models presented herein are prepared on the
The unit operates 210 d/yr
basis of publicly available and non-confidential infor Storage capacity equal to 30 days of operamation. The information and analysis are the opinions
of Intratec and do not represent the point of view of
tion for sugar and ethanol
any third parties. More information about the method Sugarcane cultivation and harvesting costs
ology for preparing this type of analysis can be found,
were not considered
$, million
thanol is a widely used commodity chemical with several applications, including

use as a solvent and as a gasoline blendstock in the fuel market. Globally, the major
portion of ethanol production is based on the
fermentation of sugars from crop feedstocks,
such as sugarcane, corn, cellulosic material
and others. World fuel ethanol production
is about 85 billion liters annually, with 60%
resulting from corn ethanol production in
the U.S., and another 25% from sugarcane
ethanol production in Brazil. In view of current
environmental issues, including greenhouse
gas emissions, fermentation-based ethanol is
considered an alternative to fossil fuels since it
originates from renewable resources.
Vent
gases
ST
1
Sugarcane
Bagasse
Electricity
1.
2.
3.
CW
14
To
waste
treatment
Lime
2
7
CW
ST
CW
10
12
CW
Phosphate
Ethanol
7
Mud
11
CW
4.
5.
6.
7.
8.
9.
10.
5
6
5
6
13.
14.
To
waste
treatment
Sulfuric acid
FIGURE 1. Traditional ethanol production process from sugarcane
11.
12.
ST
CW
13
CW
ST
Mills
Clarifier
Multiple-effect
evaporator
Vacuum calandrias
Crystallizers
Sugar centrifuges
Fermenters
Yeast centrifuge
Gas washing
column
Concentration
column
Rectifying column
Molecular sieve
unit
Cooling tower
Energy cogeneration unit
Cooling water
Steam
Ethanol from the Direct

Gasification of Biomass
Gas cleanup and conditioning. Syngas

from the gasifier is sent to the fluidized-bed
tar reformer, where the hydrocarbons are
converted to CO and H2. The deactivated
reforming catalyst is separated from the
effluent syngas in a cyclone, regenerated
and sent back to the tar reformer. The hot
syngas is used for steam generation in heat
exchangers and is then sent to the quench
tower. The cooled gas from the quench is
sent to the amine scrubber unit for the removal of CO2 and H2S. The CO2 is vented
to the atmosphere and H2S is reduced to
sulfur before disposal.
Alcohol synthesis. The treated gas is compressed and sent to the alcohol synthesis
reactor, a fixed-bed system using a MoS2based catalyst. Carbon monoxide and H2
combine through a series of reactions to
form a mixture of alcohols, with ethanol
being the main product. The reaction
products are cooled so that the mixture of
alcohols is condensed and separated from
the unconverted syngas. The unconverted
syngas is recycled to the tar reformer with
a small purge.
Alcohol separation. The condensed stream
from the alcohol synthesis reactor is vaporized and dehydrated by molecular sieves.
The dehydrated alcohol mixture is fed to
the higher alcohols column for separation
of higher alcohols as a byproduct. The
overhead from the column is then sent to the
methanol column, where ethanol product is
obtained. The column overhead, containing mainly methanol is recycled back to the
alcohol synthesis reactor.
The process
In the process of producing ethanol via direct
gasification (Figure 1), biomass is converted into synthesis gas (syngas) by partial
oxidation and the resulting stream of gases
is partially burned to produce heat for the
process and partially reacted to produce liquid alcohols. The process can be divided into
the following areas: feedstock handling and
gasification, gas cleanup and conditioning,
alcohol synthesis and alcohol separation.
Feedstock handling and gasification. The
biomass is dried with fluegas from the fuel
combustor in the biomass drier. The dried
biomass is fed into the oxygen-blown direct
gasifier with steam and high-pressure oxygen from an air-separation unit.
In the presence of steam and oxygen at
high temperature, biomass decomposes into
syngas a mixture of mostly H2 and CO,
with CH4, CO2, light hydrocarbons and
water and tar, ash and char. The combustion of a portion of the biomass supplies
the heat for the endothermic reactions. A
cyclone is used at the exit of the gasifier to
remove residual solids from the syngas.
Flue gas
250
Air
BFW

Other capital expenses
Working capital
FIGURE 2. Capital expenditures to build a plant
for ethanol
million gallons of ethanol per year erected

on the U.S. Gulf Coast
The process equipment is represented in
the simplified flowsheet in Figure 1
In the process, steam is generated through
heat recovery from hot process streams.
The power requirements for the process is
generated in turbines driven by the steam
produced
Storage capacity equal to 30 days of
operation for ethanol product
Ethanol production from biomass gasification is a promising technology that can
use a wide range of low-cost feedstocks to
produce liquid fuels. The main challenges
for the technology are the development of
mixed-alcohol catalysts, reforming and the
high investment associated with the construction of a commercial plant. n
edited by Chemical Engineering. The analyses and
CW
ST
ST
Solid
waste
Electricity
ST
5
O2
ST
BFW
CW
17
CW
CW
CW
CO 2
CW
8
16
To waste
treatment
Catalyst purge
11
100
6
1
150
ST
Biomass
200
50
The capital expense of the process was
estimated based on data from the second
quarter of 2013 (Figure 2). The following
assumptions were taken into consideration:
A biomass processing unit producing 30
Catalyst
Air
300
$, millions
ncreasing global demand for energy and

a drive to develop renewable energy
sources have focused research and
development attention on biomass (including
wood, agricultural residues and municipal
wastes) as a source of energy and products.
Biomass can be converted into bioenergy via
biochemical and thermochemical means. In
biochemical routes, the biomass is converted
into liquid or gaseous fuels by fermentation
or anaerobic digestion. In thermochemical
conversion, biomass is converted into gases
via a number of methods, and the gases
are then either used directly or synthesized
into the desired chemicals. Thermochemical
technologies include combustion, gasification and pyrolysis. This column describes a
gasification process to produce ethanol.
Flue gas
12
10
CW
9
Sulfur
ST
14
13
ST
.
FIGURE 1. Ethanol production from direct gasiication of biomass
15
ST
ST
Higher
alcohols
by-product
Ethanol
1. Biomass drier
2. Air separation unit
3. Gasifier
4. Fuel combustor
5. Tar reformer
6. Catalyst regenerator
7. Quench column
8. Amine absorber
9. Amine regenerator
10. H2S removal system
11. Compression unit
12. Alcohol synthesis reactor
13. Molecular sieve unit
14. Higher alcohols column
15. Methanol column
16. Power generation
17. Cooling tower
BFW Boiler feed water
CW Cooling water
ST Steam
Ethylene Production
via Ethanol Dehydration
thylene is arguably the most important

building block of the petrochemical
industry, frequently produced via steam
cracking of a range of petroleum-based feedstocks. Rising oil prices and concerns about
global warming have motivated research into
ethylene manufacture from renewable sources.
The green ethylene made from ethanol
(for example, from corn, sugarcane or lignocellulosic biomass) represents a chemically identical alternative to its petrochemical equivalent,
and can contribute to the overall reduction of
greenhouse gas emissions.
Ethanol dehydration
The polymer-grade (PG) ethylene production via
ethanol dehydration process depicted in the figure below was compiled based on a U.S. patent published by BP Chemicals (London, U.K.;
www.bp.com; U.S. patent no. 8,426,664).
Since 2008, BP has established more than ten
patents on this subject.
Ethanol dehydration has an overall endothermic equilibrium. The ethylene yield is favored
by higher temperatures, while lower temperatures favor production of diethyl ether (DEE).
The major process steps are outlined below.
Treatment. Fresh ethanol is combined with the
recycled ethanol and DEE from the ethylene
column and sent to the aldehyde removal column, which removes the aldehydes that came
from the fresh ethanol feed, as well as the
aldehydes and C4 hydrocarbons generated in
the reaction step.
Reaction. The bottom stream from the aldehyde removal column is sent to the feed vaporizer and superheater before being sent to the
reactors. The process uses fixed-bed reactors
with a heteropolyacid catalyst supported by
silica. The product stream from reaction is
cooled and sent to the purification section.
Purification. The reactors outlet stream
primarily consists of unreacted ethanol, water,
ethylene and DEE. The stream is sent to a
first distillation column to separate mainly the
ethylene from the water. The ethylene-rich
overhead stream is then compressed, dried
and sent to an ethylene purification column.
The bottom stream from the ethylene-water

separation column is then sent to a dewatering
column, to separate water. Streams containing
mainly ethanol and DEE are recycled back to
the treatment section.
Key research basis
The key information used as input to develop
the synthesis of the process is presented below.
The final process design was based on reasonable values from the ranges presented here.
Since the technology is in its embryonic stages,
and no commercial plant has been built using
this concept thus far, the design depicted here
is subject to changes.
Reactor temperature
200 to 250C
Reactor pressure
10 to 28 bars abs
Ethanol conversion to ethylene
(per pass)
20 to 60%
Feed ethanol water content
1 to 5 wt.%
Diethyl ether in reaction feed
50 to 85 wt.%
Catalyst-bed temperature profile
<10C
According to BP, the formation and recycling
of DEE thermodynamically favor the separation of water, and result in higher ethylene
selectivity
Moderate reaction conversion and mild
temperature and pressure conditions are
used in order to improve the selectivity for
the desired products.
conducted based on data from the second
quarter of 2012 with the U.S. Gulf Coast as
the location. The following assumptions were
assumed for the analysis:
A 190,000-ton/yr chemical production unit
(all equipment represented in the simplified
flowsheet below)
Storage capacity equal to 20 days of operation for ethanol and no storage for ethylene
O utside battery limits (OSBL) units considered: steam boilers, cooling towers,
propylene refrigeration system, control
room and administrative buildings

other capital expenses) to build an ethanol
dehydration unit would be between $200
and $280 million, and the operating cost
would be about $1,650/ton. Given that
the petroleum-based ethylene sales price is
lower than the green (via ethanol dehydration) ethylene cost of production, the green
ethylene sales price must include a premium
of more than 50% over petrochemically derived ethylene to make the venture economically feasible.
Research perspective
Strategic, financial and technical insights
about this research into the ethanol dehydration process inlcude the following:
Marketing and sales teams must ind nichemarket consumers willing to pay more for an
environmentally friendly product (for example,
plastic containers for the cosmetics industry)
Since ethanol raw material prices are dictated by markets such as food and fuel, it may
be an interesting consideration to control the
entire supply chain through the integration of
the ethanol dehydration unit with an ethanol
production unit
The published patents describe problems
related to the temperature profile of the
catalyst bed. Researchers must focus on developing a catalyst with improved tolerance
to the temperature decrease inherent in the
endothermic nature of the dehydration reaction. Higher conversion and higher selectivity
for ethylene would minimize recycling loops
and, consequently would reduce both capital
and operating costs
Diethyl ether recycle
Ethanol
RF
CW
7
By-products
to fuel
PG
ethylene
CW
ST
ST
6
CW
ST
5
2
3
10
FU
ST
Ethanol, water and diethyl ether recycle
RF
Water
1) Aldehyde removal column

2) Feed vaporizer
3) Feed superheater
4) Dehydration reactors
5) Cooler
6) Ethylene-water column
7) Compressor and drying
8) Ethylene column
9) Dewatering column
10) Propylene refrigeration unit
FU
CW
RF
ST
Fuel
Cooling water
Refrigeration fluid
Steam
Hydrogen Cyanide
Production
The process
HCN production via the Andrussow process
is depicted in Figure 1 and described below,
based on information available in the literature. The process can be divided into three
main areas: reaction, ammonia recovery and
product purification.
Reaction. Natural gas, ammonia and air are
fed into the reactor, where HCN is formed
through a catalytic reaction. The product
stream, containing HCN and unreacted ammonia, must be cooled down to avoid HCN
decomposition. This is accomplished in a
waste-heat boiler located below the reactor.
The waste-heat boiler generates steam that can
be used elsewhere in the process.
Ammonia recovery. The product stream is fed
to the bottom of the ammonia absorber, where
phosphate is used to absorb ammonia. The
overhead stream of this column, which contains
mainly HCN, is sent to the purification section.
The bottoms stream, containing ammonia and
a small amount of HCN, is heated and sent to
the first HCN stripper.
In this column, HCN is separated in the overheads and recycled to the ammonia absorber.
The bottom stream is fed to the top of the ammonia stripper, where phosphate is separated
in the bottoms. Part of this stream is mixed with
phosphoric acid and recycled to the top of the
ammonia absorber. Ammonia, now free of
phosphate, is separated as the overhead stream
of the ammonia stripper. The ammonia is then
directed to the dryer, where it is concentrated
1250
1200
Operating expenses ($/ton)
ydrogen cyanide (HCN) is a chemical

precursor used in the production of
several industrially relevant compounds,
such as adiponitrile for nylon production,
methyl methacrylate for polymer manufacturing, sodium cyanide for gold recovery and for
the production of methionine, which is used as
a feed additive.
HCN is mainly produced though the Andrussow process, named for developer Leonid
Andrussow. The method involves reacting
ammonia, natural gas and air over a platinum
catalyst to form HCN. Alternatively, HCN can
be produced by the BMA process, which uses
ammonia and natural gas only.
1150
1100
1050
1000
950
900
10
15
20
25
30
35
40
45
50
Plant capacity (thousands ton/yr)

FIGURE 2. Operating expenses for HCN production variation with plant capacity
and recycled to the reaction section.

Product purification. The HCN-containing
stream is fed to the HCN absorber, where
HCN is absorbed in cold water. The overhead
vent gas is incinerated, since it can still contain
some HCN. The bottom stream from the HCN
absorber is directed to the second HCN stripper, where the product is separated from water, and then purified in the HCN rectification
column to obtain 99.5%-pure HCN product.
operating expenses according to plant capacity is depicted in Figure 2.

Global perspective
HCN is a toxic compound and is dangerous to the environment as well as to human
health. Additionally, it is flammable and, if not
properly stored, may undergo a polymerization reaction that can be explosive. For these
reasons, HCN storage and transportation must
be avoided, so HCN is essentially a nontradable product. Companies that use HCN as
a feedstock in their processes must produce it
themselves or have it supplied to them by an
integrated HCN facility. Also, companies may
purchase HCN from nearby acrylonitrile plants
that produce it as a byproduct. n
conducted, taking the following assumptions
into consideration:
Gulf Coast (the process equipment is represented in the simplified flowsheet below)
Outside battery limits units considered are
the cooling tower and the refrigeration system
No storage was considered
The capital investment (including total fixed
investment, working capital and other capital
expenses) for the construction of this plant is
estimated to be about $80 million, while the
operating expenses are estimated to be about
$1,070 per ton of product. The variation of the

supplied by Intratec Solutions LLC (Houston; www.
represent the point of view of any third parties.
preparing this type of analysis can be found, along
Vent gas
to incineration
1 ) Reactor waste-heat boiler
CW
2 ) Ammonia absorber
6
Natural
Gas
RF
HCN
7
ST
3
NH3
make-up
ST
ST
1
ST
To waste
treatment
CW
Air
3 ) First HCN stripper

4 ) Ammonia stripper
To waste
treatment
5 ) Ammonia dryer
6 ) HCN absorber
7 ) Second HCN stripper
8 ) HCN rectification column
ST
BFW
CW
RF
4
2
9 ) Refrigeration unit
9
5
ST
Phosphoric acid
ST
ST
To waste
treatment
CW
10) Cooling tower
10

To waste
treatment
CW Cooling water
ST Steam
FIGURE 1. The HCN production scheme shown here is based on the Andrussow process
Methanol-to-Olefins Process
The process
Figure 1 illustrates an MTO process similar
to one developed jointly by UOP LLC (Des
Plaines, Ill.; www.uop.com) and Norsk
Hydro A/S (Oslo, Norway; www.hydro.
com). This process synthesizes olefins from
methanol using a SAPO-34-type zeolite catalyst in a fluidized-bed reactor. The process
can be divided into three main areas: reaction and regeneration; quench, compression
and caustic wash; and product fractionation.
Reaction and regeneration. Methanol feed is
vaporized, mixed with recovered methanol,
superheated and sent to the fluidized-bed
reactor. In the reactor, methanol is first converted to a dimethylether (DME) intermediate
and then converted to olefins with a very
high selectivity for ethylene and propylene.
During the reaction, coke accumulates
on the catalyst, which is circulated to the
fluidized-bed regenerator system. In the
regenerator, the coke is removed by combustion with air to maintain the catalyst activity.
After leaving the reactor, the reacted stream
exchanges heat with the reaction feed, in
order to recover the heat generated by the
exothermic reaction.
Quench, compression and caustic wash.
The output from the reaction and regeneration is quenched, where most of water
and unreacted methanol is removed.
The water-methanol stream is sent to the
methanol-recovery column, where methanol
is recovered and recycled to the reaction.
The vapor stream from the

quench stage is compressed
400
and sent to a caustic wash
350
column for CO2 removal.
300
The gas stream, free of
250
CO2, is then dried and sent
to the product fractionation.
200
Product fractionation.
150
The dried stream from caustic
100
wash is sent to the de-etha50
nizer column, where ethylene
0
is separated from C3 and
larger (C3+) hydrocarbons
U.S. Gulf Coast
China
as the overhead product.
FIGURE 2. Total ixed investment to build an MTO plant in
The ethylene-rich stream is
different regions
compressed and fed to the
acetylene reactor for selective acetylene
The process equipment is represented in
hydrogenation to ethane. The acetylene
the simplified flowsheet
reactor effluent is sent to the de-methanizer
The plant is constructed inside a chemical
column, where an ethylene-ethane mixture is
complex. The methanol feedstock is locally
separated from a methane-rich stream. The
provided and propylene and ethylene
ethylene-ethane mixture is then routed to the
products are consumed by nearby polyC2 splitter to obtain polymer-grade ethylene
olefins units. Therefore, no storage for
product as the overhead and an ethane-rich
product or raw material is required
stream at the bottom.
The MTO process is an alternative apThe C3+ stream from the bottom of the
proach to producing ethylene and propylde-ethanizer column is fed to the de-proene for chemical manufacturers that have
panizer column, for C4+ separation as the
access to cheap sources of methanol, which
bottom product. The de-propanizer column
can be supplied from catalytic conversion
distillate, mainly containing a propyleneof synthesis gas. Chinas low manufacturing
propane mixture, is fed to the C3 splitter
costs, as well as low investment requirecolumn. In the C3 splitter, polymer-grade
ments, explains the recent plans to construct
propylene is obtained as the overhead prod- MTO plants in the country to monetize
uct, while the bottom stream is propane-rich. excess coal resources. In the U.S. on the
other hand, methanol can be produced from
low-cost shale gas. n
The total fixed investment of the process
was estimated based on data from the
second quarter of 2013 for units erected on edited by Chemical Engineering. The analyses and
the U.S. Gulf Coast and in China (Figure
2). The following assumptions were taken
into consideration:
The plant capacity is 600,000 ton/yr of
light olefins (ethylene and propylene)
$, million
thylene and propylene are the most

important intermediates in the petrochemical industry. Globally, they are
produced mainly by steam cracking of hydrocarbons, such as naphtha, propane and ethane. The methanol-to-olefins (MTO) process is
an alternative approach to producing these
light olefins from methanol feedstock, which
can be derived from other raw materials,
including natural gas, coal or biomass.
Tail gas
RF
Regen gas
RF
RF
8
1
1
Process
water
Methanol
CW
10
7
ST
Ethane
ST
ST
CW
Air
ST
To waste
CW
CW
Caustic
soda
Ethylene
PG Propylene
12
11
ST
ST
RF
Water
13
CW
14
ST
15
FIGURE 1. Methanol-to-oleins technology similar to UOP/Hydro MTO process
ST
Propane
+
4
C byproduct
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
Reactor
Regenerator
Quench tower
Compression
Methanol recovery column
Caustic wash column
Deethanizer column
Acetylene reactor
Demethanizer
C2 splitter
Depropanizer
C3 splitter
Refrigeration unit
Cooling tower
Boiler
CW Cooling water
ST Steam
Methanol-to-Propylene
Technology
The process
The MTP process consists basically of two
reaction steps: an initial one to dehydrate
methanol to dimethyl ether (DME) on an
aluminum oxide catalyst, and a second one
to transform DME and methanol into a variety
of olefins, ranging from ethylene to octenes.
However, using a zeolite-based catalyst (ZSM5), the process yields mainly propylene. A set
of purification columns is necessary to obtain
the polymer-grade (PG) propylene.
Figure 1 illustrates a process similar to the
ones licensed by Lurgi GmbH (the MTP process; Frankfurt am Main, Germany; www.lurgi.
com) and JGC Corp. (Yokohama, Japan; www.
jgc.co.jp) and Mitsubishi Chemical Corp.s
(Tokyo; www.mitsubishichemical.com) DTP
process, which can be divided into three main
areas: reaction and regeneration; quench and
compression; and product fractionation.
Reaction and regeneration. In this stage,
the methanol feed is vaporized, mixed with
recovered methanol and dimethyl ether (DME),
superheated and sent to the DME reactor,
where dehydration occurs.
The product is mixed with recycled hydrocarbons and steam before being fed into the
MTP reactors. The reactors were designed with
several stages to better approach isothermal
conditions. Propylene synthesis is conducted
in multiple reactors: while one set of reactors
conducts the reaction, the remaining ones are
in regeneration or on stand-by mode. The recy-
conducted based on data from the fourth quarter of 2012. The following assumptions were
taken into consideration:
Gulf Coast (the process equipment is represented in the simplified flowsheet)
There is no storage for feedstock and product
Outside battery limits (OSBL) units considered: propylene refrigeration system
other capital expenses) to build the MTP plant
Raw materials costs

Main utilities consumptions
Fixed costs
1,800
1,600
$/metric ton of product
cling of olefins increases propylene yield and

absorbs the heat generated in the reaction.
After leaving the reactors, the mixture is
cooled and sent to the quench and compression steps.
Quench and compression. The output from
the reactors is quenched, where most of the
water is removed. A portion of this water is
sent to the methanol-recovery column, while
the remaining water is vaporized and used as
dilution steam in the MTP reactors. The vapor
stream from the quench stage is compressed,
partially condensed and then separated into
liquid and vapor streams.
Product fractionation. The liquid stream from
the quench and compression stages is sent to
the debutanizer, to separate four-carbon C4
hydrocarbons (and those with less than four
carbons) and DME from those with greater
than five carbons (C5+ components). The C5+
stream from the column bottom is then separated (in the dehexanizer) into a C5/C6 stream
that is to be recycled to the MTP reactors and
into a heavier-hydrocarbons stream (gasoline).
The debutanizer overhead stream is mixed
with the vapor stream from the compression
stage and sent to the DME removal system. The
system overhead product, mainly propylene,
is sent to the de-ethanizer, while the bottom
is mostly recycled. The bottoms from the deethanizer is routed to the C3 splitter, to obtain
polymer-grade propylene, while the overhead
is recycled to the MTP reactors. The bottoms
material from the C3 splitter is purged as liquid
petroleum gas (LPG).
ropylene has been established as an

important part of the global olefins business, trailing only ethylene in terms of
volume of product. Because inexpensive natural gas from shale in the U.S. is increasingly
used as a feedstock for producing ethylene,
lower quantities of three- and four-carbon olefins are available. For this reason, new chemical processes for on-purpose propylene using
low-cost raw materials are gaining importance.
An example of such a process is methanol-topropylene (MTP) technology.
The main raw material used in the MTP
process is methanol that is produced from
synthesis gas which, in turn, can be obtained
in large-scale from natural gas or coal.
1,400
1,200
1,000
800
600
400
200
0
U.S. Gulf
Coast
FIGURE 2. Both China and the U.S. are favorable regions for MTP plants because of coal in
China and shale gas in the U.S.
is about $370 million. The capital investment

for a similar plant built in China is about $295
million. Figure 2 illustrates the operating costs
for both regions.
Currently, the existing MTP commercial
units were constructed in China, inside huge
complexes, where coal is extracted and
transformed to synthesis gas, which is used to
synthesize methanol in high-capacity facilities
(over 1 million ton/yr of methanol).
China possesses large reserves of coal,
making it a favorable region for MTP plants.
In the U.S., the growing availability of natural
gas extracted from shale guarantees the
availability of synthesis gas to produce the
methanol required for the MTP process. Therefore, the country is also a promising region for
future MTP units.
Fuel gas
Methanol
RF
CW
Recycle 3
ST
6
1
CW
10
ST
Recycles
1, 2 and 3
CW
ST
Recycle 1
CW
5
ST
PG Propylene
ST
11
CW
CW
CW
3. Quench
4. Compression
5. Methanol recovery
column
6. DME removal
system (col.1)
7. DME removal
system (col.2)
8. Debutanizer column
10. Deethanizer column
ST
LPG
1. DME reactor
2. MTP reactors
9. Dehexanizer column
CW
Recycle 2
China
11. Propylene-propane
splitter
12. Refrigeration unit
9
CW Cooling water
ST
Water
ST
ST
RF
12
FIGURE 1. Propylene production from methanol, according to a process similar to the Lurgi MTP and JGC Mitsubishi DTP processes
ST Steam
Polypropylene Production via GasPhase Process: Stirred-bed reactor

The process
Propylene conversion to polypropylene is
achieved through the use of a Ziegler-Natta
catalyst. This process occurs in a continuous
vertical stirred reactor at mild temperatures
(about 80C). The overall yields are typically
>99 wt.%. The process can be divided in three
main areas: purification and reaction; resin
degassing and pelletizing; and vent recovery.
Purification and reaction. The polymerization
catalysts are sensitive to several impurities,
such as oxygen and water. To meet these
Catalyst
Cocatalyst
CW
1
4
H2
300,000
exposure restrictions, purification equipment is used
before the reaction.
250,000
In the polymerizaProject
tion area, fresh purified
contingency
propylene is mixed with a
200,000
Indirect project
recycled monomer stream
expenses
and is fed to the reactor
150,000
Direct project
along with the catalyst,
expenses
co-catalyst and hydrogen.
The heat of polymerization
100,000
is removed from the reactor
by condensing propylene
50,000
gas from the top of the
reactor and recycling
the liquid back into the
0
agitated reactor.
Integrated
Non-integrated
Resin degassing and pelscenario
scenario
letizing. The outlet reactor
stream goes to a discharge FIGURE 2. Total ixed investment according to integration scenario
vessel to be separated.
The polymer powder is sent to a purge vessel,
while the carrier gas goes through a cyclone
conducted based on data from the first quarter
and a filter and is finally sent for recovery.
of 2013 for a plant with a nominal capacity
Nitrogen is used to remove residual monomer
of 300,000 ton/yr, erected in the U.S. Gulf
from the polymer powder and then the N2
Coast region (the required process equipment
gas is also sent for recovery.
is represented in the simplified flowsheet). Two
The polymer powder then goes to a screw
scenarios were analyzed:
extruder, where the powder and additives are
1) Integrated scenario. This case is based on
melted, compounded and homogenized. After
the construction of a plant linked to a propylbeing extruded, the pellets are carried to a
ene supplier. In this scenario, the nearby unit
centrifugal dryer.
continuously provides propylene, and receives
Vent recovery. The carrier gas is compressed
impure propylene for purification. Thus, no
and one portion of it is sent back to the reacstorage for propylene is required. However,
tor. The other portion is sent to a recovery
storage of products is equal to 20 days of
unit. The nitrogen and propylene streams
operation.
from the purge vessel are recovered and
2) Non-integrated scenario. This case corseparated in a membrane unit. The nitrogen
responds to a grassroots unit. Thus, 20 days
is recovered to the process, while the monoof operation was considered for both products
mer goes to a propylene-propane splitter
and raw materials. In addition, this scenario
(inside the purification area of the propylene
includes a propane-propylene splitter.
supplier, if the plant is part of a petrochemiThe level of integration is a key factor in this
cal complex).
process, since it can determine
whether the process is profitable
or not. The level of integration
Propylene
(1) Reactor
causes the total fixed investment
CW
suppliers
(2) Fixed-bed dryers
(Figure 2) and manufacturing
purification
expenses to vary greatly. In terms
area (integrated
(3) Discharge vessel
of manufacturing expenses, in
petrochemical
(4) Purge vessel
process)
non-integrated plants, propylene
is purchased at higher prices,
(5) Extruder
while in integrated complexes, it
Membrane
(6) Centrifugal dryer
can be obtained directly from the
recovery
Offgas
supplier at a lower cost. n
(7) Compression
to flare
system
U.S. dollars, thousands
ince 1956, polypropylene has been

commercially produced using catalysts
and technology that were developed
from independent research by Karl Ziegler and
Giulio Natta. Their namesake catalysts have
enabled the widespread use of this polymer in
the decades since. Polypropylene has become
a major part of the modern plastics-resin
market because of its unique physical properties, and is now employed in a wide range of
applications from food packaging to automotive plastics.
Historically, polypropylene has been
produced at industrial scale by three main
polymerization approaches: hydrocarbon
slurry or suspension processes, bulk-phase
processes and gas-phase processes. Two
leading technologies for gas-phase polypropylene production are Unipol, a fluidized-bed
reactor process offered by the Dow Chemical Co. (Midland, Mich.; www.dow.com),
and Novolen, a stirred-bed reactor process
developed by Lummus Novolen, now a part
of Chicago Bridge and Iron Co. N.V. (The
Hague, The Netherlands; www.cbi.com). A
process similar to Unipol was discussed in this
column last year (Chem. Eng., May 2013, p.
33). Here, Figure 1 depicts a gas-phase process similar to Lummus Novolens stirred-bed
reactor technology.
(8) Cooling tower
N2
CW: Cooling water

CW
2
Additives
6
Fresh
propylene
Polypropylene
pellets
FIGURE 1. Polypropylene production via a gas-phase process similar to that of Lummus Novolen
Editors Note: The content for this column is supplied by Intratec Solutions
LLC (Houston; www.intratec.us) and
edited by Chemical Engineering. The
analyses and models presented herein
are prepared on the basis of publicly
available and non-confidential information. The information and analysis
are the opinions of Intratec and do not
represent the point of view of any third
parties. More information about the
methodology for preparing this type
of analysis can be found, along with
terms of use, at www.intratec.us/che.
Polypropylene BulkPhase Process

and is then dried. Following that,

the product is combined with adWorking capital
ditives and then flows to the pelOther capital expenses
letizing unit. The polymer pellets
are cooled and sent to a product
400
blending-and-storage system. The
350
monomer stream that is recovered
from the steam-treatment vessel
300
is sent to a scrubber for water
removal.
250
Monomer recovery. The gas from
200
the high-pressure degasser is directly sent to the propylene scrub150
ber. The propylene-recovered
streams from the steam scrubber
100
and low-pressure degasser are
50
washed with an anti-fouling agent
before being compressed and
0
sent to the propylene scrubber,
Non-integrated
Integrated
where the monomer is separated from polymer residues and
recycled to the reaction area. A
FIGURE 2. An economic comparison of polypropylene
fraction of the recycle monomer
production can be made between an integrated and nonstream is sent to a propylene-propane integrated scenario
splitter column (inside the purification
responds to a grassroots unit. Thus, 20 days
area of the propylene supplier, if the plant is
of operation was considered for both products
part of an integrated petrochemical complex)
and raw materials. In addition, this scenario
for purification.
includes a propane-propylene splitter.
The level of integration with nearby facilities
significantly impacts the capital expenses
An economic evaluation of the bulk-phase
required for the construction of a PP plant. The
polypropylene process was conducted, based
chart (Figure 2) shows the evaluation of capital
on data from the fourth quarter of 2012. The
expenses for both scenarios. Furthermore, the
evaluation concerns a plant with a nominal caelevated market prices for propylene makes it
pacity of 350,000 ton/yr erected in the U.S.
unprofitable to operate a stand-alone PP unit
Gulf Coast region (the required process equipin the U.S., when compared to the propylene
ment is represented in the simplified flowsheet).
production cost of integrated plants.
Two scenarios were analyzed:
1) Integrated scenario. This case corresponds
U.S. dollars, millions
olypropylene (PP) is a thermoplastic

polymer formed by the polymerization of 10,00020,000 monomers of
propylene. With a global market of about 60
million metric tons per year, PP is the second
most-used polymer globally.
More than 35% of the worlds total PP is produced using LyondellBasells (Houston; www.
lyondellbasell.com) Spheripol technology.
The process
In Spheripol technology, polymerization is
carried out in liquid propylene (a bulk-slurry
process) in tubular loop reactors. This type of
reactor has a high heat-removal capacity and
avoids polymer deposition on reactor walls.
A polypropylene homopolymer production
process via a bulk-slurry process similar to
LyondellBasell Spheripol is depicted in the
flowsheet (Figure 1). The process shown is
capable of producing both homopolymer and
random copolymer PP. For impact copolymer production, the addition of a gas-phase
reactor is required. In this process, liquid
propylene contacts a solid catalyst inside a
loop reactor. The process can be separated
into three main areas: purification and reaction; polymer degassing and pelletizing; and
monomer recovery.
Reaction and purification. In this stage,
fresh polymer grade (PG) propylene is sent
to fixed-bed dryers for removal of water
and other potential catalyst poisons. The
catalyst and part of the purified propylene
are continuously fed to the prepolymerization
reactor. This forms a protective shell around
the catalyst particle, which decreases the occurrence of fouling. The remaining fresh and
recovered propylene are fed into two loop
reactors in series. In the case of copolymer
production, ethylene comonomer is also
added to the reactors.
Polymer degassing and pelletizing. The slurry
from the reactor is discharged into two pressure vessels to separate the unreacted monomer from the polymer. The polymer receives
a steam treatment to deactivate the catalyst,
to a PP plant that is linked to a propylene

supplier. This nearby unit continuously provides
PG propylene at prices below the market
average, and receives impure propylene for
purification. Thus, no storage for propylene
is required. However, storage of products is
equal to 20 days of operation.
2) Non-integrated scenario. This case cor-

Intratec Solutions LLC (Houston; www.intratec.us) and edited
by Chemical Engineering. The analyses and models presented
herein are prepared on the basis of publicly available and
non-confidential information. The information and analysis are
the opinions of Intratec and do not represent the point of view
of any third parties. More information about the methodology
for preparing this type of analysis can be found, along with
terms of use, at www.intratec.us/che.
(1) Fixed bed dryer

(2) Loop reactors
CW
(3) High pressure degasser

(4) Low pressure degasser
CW
2
CW
(5) Steam treatment vessel
N2 purge 10
Catalyst and
chemicals
ST
To waste oil
tank
CW
PG propylene
(7) Extruder and pelletizing

(8) Steam scrubber
(9) Drying gas scrubber
(10) Low-pressure propylene
scrubber
CW
ST
To water
treatment
N2
(11) Propylene scrubber

(12) Cooling tower
(13) Boiler
Additives
6
Propylene suppliers
purification area (integrated
petrochemical process)
(6) Hot nitrogen dryer
Anti-fouling
agent
11
CW
Polypropylene
CW
12 ST
13
CW: Cooling water

ST: Steam
FIGURE 1. Over 35% of the world's polypropylene is produced using LyondellBasell's Spheripol (similar to the bulk-phase process shown)
Polypropylene Production
via Gas-Phase Process
The process
PP is a thermoplastic material formed by the polymerization of propylene, resulting in a macromolecule that contains from 10,000 to 20,000
monomer units. The production of a polypropylene homopolymer via a
gas-phase process similar to Dow Unipol is depicted in the diagram (Figure 1). The process shown is capable of producting homopolymer and
random copolymer PP. For impact copolymer production, a secondary
reaction loop is required. In this process, gaseous propylene contacts a
solid catalyst in a fluidized-bed reactor. The process can be separated
into three different areas: purification and reaction; resin degassing and
pelletizing; and vent recovery.
Purification and reaction. Fresh polymer grade (PG) propylene is sent
to fixed-bed dryers to remove water and other polar impurities. The
purified propylene, a recycle stream from the vent recovery system and
comonomers (in case of copolymer production) are then fed continuously to the reactor. A gas compressor circulates reaction gas upward
through the reactor, providing the agitation required for fluidization,
backmixing and heat removal. No mechanical stirrers or agitators are
required in the process reactor. The overhead gas from the reactor
passes through a cooler for reaction heat removal. Catalyst is continuously fed to the reactor.
Resin degassing and pelletizing. Resulting granular polypropylene is
removed from the reactor by the discharge tanks and sent to a purge
bin where residual hydrocarbons are stripped with nitrogen from the
resin and are sent to the vent recovery system. The resin from purge bin
is combined with additives and then flows to the pelletizing unit. The
pellets are dried, cooled and sent to product blending and storage.
Vent recovery. The vent gas is processed to separate hydrocarbons and
nitrogen purge gas, which is returned to the process. The condensed
components are separated into a propylene stream, which is returned to
the reaction system, and a propane stream.
An economic evaluation of the process was conducted for two distinct
integration scenarios:
Total fixed investment costs

Direct
expenses
Indirect
expenses
Project
contingency
350,000
300,000
$, thousands
olypropylene (PP) is one of the worlds most widely used polymers, second only to polyethylene in terms of global demand. The
global market for polypropylene is over 60 million metric tons per
year, and it is utilized in a broad and diverse range of end-uses from
injection-molding applications to films and sheets, as well as synthetic
raffia and other fibers, among others. Traditionally, the most representative types of propylene polymerization are the following: hydrocarbon
slurry or suspension, bulk (or bulk slurry), gas phase and hybrid (uses
bulk- and gas-phase polymerization reactors).
The Unipol PP process, a leading gas-phase process technology, was
recently offered for sale by Dow Chemical Co. (Midland, Mich.; www.
dow.com). The company is looking to focus on high-margin areas, and is
seeking buyers for its polypropylene licensing and catalyst business.
250,000
200,000
150,000
100,000
50,000
0
Non-integrated scenario
Integrated scenario
FIGURE 2. Elevated propylene prices make it unproitable to operate a

standalone PP unit
The integrated scenario is based on the construction of a plant linked

to a propylene supplier. In this case, storage for propylene is not required. However, the estimated investment for the integrated scenario
includes storage for PP equivalent to 20 days of plant operation
The non-integrated scenario is based on the construction of a grassroots PP processing unit. Thus, a time period of 20 days of operation
was considered for storage of both products and raw materials
The economic evaluation was based on data from the third quarter of
2011 and a plant nominal capacity of 400,000 ton/yr erected on the
U.S. Gulf Coast (only the process equipment is represented in the simplified flowsheet).
The level of integration with nearby facilities significantly impacts
the total fixed investment required for the construction of a PP plant, as
represented in the graph (Figure 2).
More than that, the elevated market prices for propylene in the U.S.
make it unprofitable to operate a stand-alone PP unit. However, PP units
that are integrated upstream with a propylene production plant may purchase propylene at prices below the market average, reaching EBITDA
(earnings before interest, taxes, depreciation and amortization) margins
of above 20%.
Editors Note: The content for this column is supplied by Intratec Solutions LLC
(Houston; www.intratec.us) and edited by Chemical Engineering. The analyses
and models presented herein are prepared on the basis of publicly available and
non-confidential information. The information and analysis are the opinions of
Intratec and do not represent the point of view of any third parties. More information about the methodology for preparing this type of analysis can be found, along
CW
1. Fixed-bed dryer
2. Polymerization reactor
3. Gas compression and cooling
4. Discharge and blowdown tanks

9
5. Purge bin
CW
6. Horizontal ribbon blender

ST
Additives
1
Propane
purge
PG propylene
FIGURE 1. Homopolymer PP production process similar to Dow Unipol
8. Centrifugal dryer
9. P-P splitter
CW Cooling water
ST
4
Catalyst and
additives
7. Extruder and pelletizer
Polypropylene
pellets
Steam
Propylene Production
via Metathesis
ropylene is typically considered a co-product in steam

crackers and fluid-catalytic-cracking (FCC) processes,
which are primarily driven by ethylene and motor gasoline production, respectively.
Recently, most U.S. ethylene producers have shifted to
lighter feedstocks due to the availability of low-cost natural
gas and natural-gas liquids (NGLs) from shale. This shift
drastically decreases propylene byproduct output. Since
propylene demand is growing faster than that of ethylene,
and is expected to continue increasing, a gap between propylene supply and demand is arising. This brings about the
possibility of establishing chemical processes for on-purpose
propylene production, and one of the processes depends on
metathesis chemistry.
For
disposal
FIGURE 1.
Fresh ethylene
Fresh butene
1
FU
(1) Reactor feed treater

(2) Reactor feed heater
(3) Metathesis reactor
3'
FU
Lights to fuel
RF
CW
(4) Regeneration gas heater
The metathesis process

(5) Deethylenizer column
PG
Metathesis, also known as disproportionation, is a reversible
propylene
(6) Depropylenizer column
reaction between ethylene and butenes in which carbon5
6
carbon double bonds are broken and then rearranged to form
propylene. Both ethylene and 2-butenes are mainly supplied
FU: fuel
from steam-cracker units, but can also be obtained from FCC
CW: cooling water
units. The metathesis process depicted in Figure 1 is similar to
ST
ST
RF: refrigeration fluid
the OCT (olefins conversion technology) process developed by
ST:
steam
Lummus Technology (part of Chicago Bridge & Iron Co. N.V.;
the Hague, The Netherlands; www.cbi.com) and makes use
Heavies to fuel
of a tungsten oxide catalyst, along with a magnesium oxide
lion, the lowest among the regions compared. Germany presented a
co-catalyst. The OCT process typically achieves a propylene yield of
higher capital investment $295 million but the lowest operating
about 90%.
cost, at about $1,320/ton, compared to $1,480/ton in the U.S. In
The process is divided into two main areas: purification and reaction;
Brazil, both the initial capital investment for a metathesis plant and the
and separation.
operating costs were the highest.
Puriication and reaction section. Fresh and recycled ethylene and
butene are mixed and fed to treatment equipment that removes potential
Global perspective
catalyst poisons, such as oxygenates and sulfur. After treatment, the
Despite the higher operating costs, metathesis plants in the U.S. have
stream is vaporized and heated to the reaction temperature, between
exhibited the highest EBITDA (earnings before interest, taxes, deprecia280 and 320C. The metathesis reaction occurs in a fixed-bed catalytic
tion and amortization) margins, since the propylene product prices in
reactor, and butene is commonly employed in excess to minimize evenNorth America were higher than those in Europe.
tual side reactions that produce mostly five- to eight-carbon olefins. Coke,
The higher EBITDA, coupled with the lowest total capital investment,
another byproduct of the reaction, is deposited on the catalyst throughout
makes the U.S. the most promising region for new metathesis projects.
the process. Each reactor can run for about 30 days before requiring
However, the current number of metathesis units worldwide shows that
regeneration, where coke is burned off in a controlled atmosphere.
such units can also be profitable outside the U.S., as shown in the world
Separation section. Propylene purification is carried out in two columns. The stream leaving the reactor is cooled and sent to the deethylenmap (Figure 2).
izer column, the overhead stream is recycled back to the reactor and
the bottom stream is fed to the depropylenizer column, which produces
polymer-grade propylene in the overhead, as well as a heavies product
stream (four-carbon compounds and greater) that is also recycled.
(Houston; www.intratec.us) and edited by Chemical Engineering. The analyses and
An economic evaluation of the process was conducted for three distinct
locations the U.S. Gulf Coast region, Germany and Brazil and
is based on data from the third quarter of
2011. The following assumptions were taken
FIGURE 2.
into consideration:
Each mark in the
A 350,000 ton/yr metathesis unit erected
map corresponds
to an existing
inside a petrochemical complex (all equipmetathesis plant.
ment is represented in the simplified
The nominal
flowsheet in Figure 1)
capacity of each
Storage cost of the main product is equal
plant follows the
to 20 days of operation, and storage cost
legend below:
for feedstocks was not considered
The excess fuel gas generated in the process is considered to be sold to a nearby
Up to 149,000 ton/yr
chemical plant at natural gas prices
models presented herein are prepared on the basis of publicly available and nonconfidential information. The information and analysis are the opinions of Intratec
and do not represent the point of view of any third parties. More information about
the methodology for preparing this type of analysis can be found, along with terms
of use, at www.intratec.us/che.
From 150,000 to 199,000 ton/yr

total fixed investment, other capital expenses
and working capital) and for such a plant
on the U.S. Gulf Coast is about $245 mil-
From 200,000 to 249,000 ton/yr

At least 250,000 ton/yr
Propylene Production via

Propane Dehydrogenation
ecause natural gas supplies are significantly increasing due to

the rising exploitation of shale gas, mainly in the U.S., propane
prices are decreasing. Coupled with low propane prices, ethylene producers are shifting to lighter feedstocks (more ethane, less naphtha), which is decreasing yields of propylene in cracking operations.
The increasing demand for propylene and the availability of low-cost
feedstock make propane dehydrogenation an economically attractive
chemical route.
Propane, the main feedstock for propane dehydrogenation (PDH)
processes, can be obtained as a byproduct of petroleum refinery operations and can be recovered from propane-rich liquefied petroleum gas
(LPG) streams from natural-gas processing plants.
Regional cost comparison

Net raw
materials costs
$/million ton product
1,400
Main utilities
consumptions
1,200
1,000
800
600
400
200
0
US Gulf
The PDH process

PDH is an endothermic equilibrium reaction. The PDH process depicted
below is similar to the Oleflex process developed by UOP LLC (Des
Plaines, Ill.; www.uop.com), and is suited to produce polymer-grade
(PG) propylene from propane. The maximum unit capacity is around
650,000 ton/yr. This process is carried out in the presence of a platinum catalyst and achieves overall propylene yields of about 90 wt.%.
The industrial plant can be divided into two main sections: reaction
and product recovery.
Reaction. In the reaction section, after heavy impurities removal in
the de-oiler column, propane is sent to the dehydrogenation reactors.
The propylene yield in such reactors is favored by higher temperatures
and lower pressures. However, temperatures that are too elevated will
promote thermal cracking reactions that generate undesirable byproducts. Therefore, the PDH reaction usually occurs at temperatures of about
650C and near atmospheric pressures.
In order to purge the coke accumulated on the catalyst surface during
the reaction, a continuous catalyst regenerator (CCR) unit is required. The
catalyst circulates in moving beds through the reactors, before being fed
to the CCR unit, which operates independently of the reaction, burning off
the coke and returning the catalyst to its reduced state.
Product recovery. The reactor effluent is compressed, dried and sent to
the product recovery section. In this section, a hydrogen-rich stream is
recovered and light hydrocarbons and hydrogen traces are removed
in a de-ethanizer. The PG propylene product is further purified in a
propane-propylene (PP) splitter and leaves as the top product.
Brazil
China
Total capital investment

Total fixed
investment (TFI)
Working
capital
$, millions
600
500
400
300
200
US Gulf
Brazil
China
Global perspective
Recently, conditions in the U.S. have led to the lowest production costs
and the most attractive EBITDA (earnings before interest, taxes, depreciation and amortization) margins (about 30%), due to the availability
of low-cost propane derived from shale gas. Low-cost propane imported
from the Middle East allows China to present favorable EBITDA margins
of about 20%. The optimism about this process is demonstrated by the
recently announced plans for at least six PDH units in China.
Considering the capital-cost requirements presented and an operating
rate of 91%, the internal rate of return is above 30% in the U.S. and
about 20% in China.
On the other hand, South America and Europe do not offer favorable
conditions for PDH units.
Editors Note:
The content for this column is supplied by Intratec Solutions LLC. (Houston; www.
intratec.us) and edited by Chemical Engineering. The analyses and models presented herein are prepared on the basis of publicly available and non-confidential
information. The information and analysis are the opinions of Intratec and do not
represent the point of view of any third parties. More information about the methodology for preparing this type of analysis can be found, along with terms of use,
at www.intratec.us/che.
Lights to fuel
5
PG propylene
RF
4
RF
CW : Cooling water
CCR: continuous catalyst regeneration
RF: Refrigeration fluid
ST: Steam
PSA: pressure-swing absorption
(8) Deethanizer
(9) P-P Splitter
(10) Deoiler
ST
(11) C3= Refrigeration unit
10
FU: Fuel
(5) Cold box

(6) PSA
(7) Selective hydrogenation
11
FU
7
(2) Reactor heaters

(4) Compression & drying
(1) Reactors
(3) CCR
CW
Fresh propane
Other
700
An economic evaluation of the process was conducted based on data
from the second quarter of 2012. The following assumptions are assumed for the analysis:
A 550,000 ton/yr PDH unit erected inside a petrochemical complex
(all equipment represented in the simplified flowsheet below)
No storage of feedstock and product is considered
Net raw materials cost is the difference between propane and catalyst
make-up costs and credits from fuel and electricity generated in the
process
Fixed
costs
Heavies
to fuel
Catalyst flow
Sodium Hypochlorite
Chemical Production
13
Bleach concentration, trade %
odium hypochlorite (NaClO) is the active constituent in chlorine bleach, a strong oxidizer and
bleaching agent. Increases in household bleach
demand are driven mostly by population growth. In
turn, population growth and its corresponding increases
in water consumption coupled with limited fresh
water resources makes water treatment the largest
application for bleach, as well as the fastest-growing
segment of bleach use.
Sodium hypochlorite chemical production is a wellestablished process in the industry, and the principle
behind its operation is also employed for preventing
chlorine emissions in chlor-alkali plants. The chemical
process relies on the acquisition of chlorine and caustic
soda (sodium hydroxide; NaOH) feedstock from external sources, in contrast with the electrochemical process
for bleach, which also involves brine electrolysis.
12
11
10
9
8
7
6
5
20
40
15 C
The process
The chlorination of caustic soda to sodium hypochlorite is an exothermic reaction. The chemical production process depicted below is a
widely used process, similar to the one employed by Solvay Chemicals
(Brussels, Belgium; www.solvay.com), for example. The process is suited
to producing both household bleach (56 wt.%) and industrial bleach
(1015 wt.%), and relies on the chlorination of caustic soda by chlorine
gas within packed columns.
The industrial sodium-hypochlorite plant can be divided into two main
sections: reaction and product discharge; and bleach filtration.
Reaction and product discharge. The chlorine absorption system can
be divided into two parts: in the first, a packed column is operated
with a safe excess of caustic to prevent reduction in pH; the second
part, in turn, receives the liquor from the first column to be postchlorinated, until the desired bleach concentration is reached. Prior
to reaction, caustic soda is diluted with water in the first buffer tank,
along with the first-column bottom stream. Chlorine gas is diluted
with air and fed into the bottom of both columns. Flow to the second
part of the system is established when the finished product is sent to
the filtration steps.
Bleach filtration. Bleach filtration is necessary to meet product quality requirements and is often the last step before storage. Usually, the bleach
filter system consists of pressure-leaf filters. After filtration, the product is
sent to storage. Backwash water containing spent filter aid can be taken
to a dry-cake pressure filter for further processing.
Sodium hypochlorite solutions are very sensitive and special operations must be carried out to prevent its decomposition. Besides pH,
other factors affecting degradation are the initial bleach concentration,
exposure to ultraviolet light, presence of certain metals and elevated
20 C
(1) 1st Absorption

column
CW
Backwash
water to
disposal
Chlorine
Air
(2) 1st Buffer

tank
(3) 2nd Absorption
column
(4) 2nd Buffer
tank
Water
2
30 C
120
40 C
Global perspective
Selling prices for bleach vary substantially, depending on supply and
demand luctuations of the chlorine/caustic market. Based on the
estimated capital and operating costs, a U.S. Gulf Coast-based bleach
manufacturing venture can reach an internal rate of return (IRR) above
15%, by selling bleach at an average price of $175/ton, a reasonable
value. However, a venture in Germany would not be economically attractive at the same selling price.
Caustic soda
100
An economic evaluation of the process was conducted for three distinct
locations the U.S. Gulf Coast region, Germany and Brazil and is
based on data from the first quarter of 2012. The following assumptions
are made for the analysis:
A 250,000 ton/yr chemical production unit (NaClO solution, 12.5
wt. %) erected inside a chlor-alkali facility (all equipment is represented in the simplified flowsheet)
Storage of products is equal to 20 days of operation, and there is no
storage for feedstock
The estimated capital investment for such a plant on the U.S. Gulf Coast
is about $35 million, the lowest among the regions compared. Germany
presented a higher capital investment, at $40 million, and the highest
operating costs about $170/ton (compared to $140/ton in the U.S.)
6
1
25 C
80
temperatures. The graph above shows temperature dependency for

bleach degradation, starting from a 12.5 trade-percent solution. Trade
percent is an expression of available chlorine, in units of grams per liter
of available chlorine.
Offgas to
scrubber
CW
60
Time, days
Bleach
to storage
(5) Bleach filter

system
(6) Backwash
water filter
CW = Cooling
water
Editors Note: The content

for this column is supplied
by Intratec Solutions LLC
(Houston; www.intratec.
us) and edited by Chemical
Engineering. The analyses
and models presented herein
are prepared on the basis of
publicly available and nonconfidential information. The
information and analysis are
the opinions of Intratec and
do not represent the point
of view of any third parties.
More information about the
methodology for preparing
this type of analysis can be
found, along with terms of
use, at www.intratec.us/che.
n-Butanol from
Lignocellulosic Feedstock
he alcohol n-butanol is applied in the production of butyl acrylates

to supply the coatings and adhesives industries. It is also used in
plasticizers or directly as a solvent. It is commercially produced
from propylene and synthesis gas (syngas) by chemical synthesis.
Due to the increasing interest in biofuels development, the production of n-butanol through a fermentation process is being revisited
and improved. Biobutanol is an attractive renewable fuel that can be
produced from the fermentation of sugars derived from agricultural
feedstock for example, corn and sugarcane or from waste lignocellulosic materials, such as corn stover and sugarcane bagasse.
In this field, bio-butanol is viewed as an alternative to ethanol, since
it fits the existing fuel infrastructure better and exhibits higher energy
content, which makes it a more suitable gasoline blending fuel.
The process
The production process for n-butanol from corn stover via acetonebutanol-ethanol (ABE) fermentation is depicted in Figure 1. The feed
handling, pretreatment and fermentation steps were compiled from a
technical report published by the National Renewable Energy Laboratory (Golden, Colo.; www.nrel.gov; NREL/TP-5100-47764, May 2011)
and adapted for n-butanol production. The purification step was based
on typical ABE fermentation processes.
Feed handling. Corn-stover supply trucks send the biomass to weighting
and unloading stations, followed by a short-term queuing storage and
conveyors for feeding the feedstock to the pretreatment area.
Pretreatment. The biomass, composed of cellulose, hemicellulose and
lignin, is treated with dilute sulfuric acid and heated in a screw-feed
reactor to convert most of the hemicellulose into fermentable sugar, such
as xylose. After pretreatment, the solution is flash-cooled, and water is
removed, condensed and sent to the wastewater-treatment area. The mixture is then diluted with water and its pH adjusted by adding ammonia.
Hydrolysis and fermentation. In this step, cellulose is converted to
fermentable glucose using enzymes. The hydrolysis is initiated in a
continuous reactor and completed in several parallel batch fermenters.
The slurry is then cooled and inoculated with microorganisms, which
convert xylose and glucose into acetone, ethanol and n-butanol. The
fermentation beer is then sent to the beer well before being directed to
the purification section.
Purification. The fermentation beer is separated into acetone, ethanol
and n-butanol products by a series of distillation columns, a decanter
and a molecular sieve unit (to purify ethanol to commercial grade). The
bottoms of the beer column, containing water and lignin, is sent to a
filter. The filtrate is directed to the wastewater-treatment apparatus. The
residues from wastewater treatment and lignin from filtration are burned
for steam and electricity generation. The distillate from the n-butanol column is recycled to the acetone column to improve n-butanol recovery.
Corn Stover
n Acrylate
n Glycol ethers
n Acetate
n Plasticizer
n Other
n Amino resins
2%
2%
1%
An economic evaluation of the process was conducted taking into
consideration a facility located on the U.S. Gulf Coast that is capable
of producing 100,000 ton/yr of bio-butanol, 10,000 ton/yr of acetone
and 8,000 ton/yr of ethanol.
The total estimated investment (including total fixed investment, working capital and initial expenses) for this plant is about $450 million,
while the operating expenses are about $1,000/ton of n-butanol.
Global perspective
In the past, the ABE fermentation was used to commercially produce
acetone and n-butanol, but this process fell out of favor because petrochemical processes became more cost-effective.
Still, the production of bio-butanol from ABE fermentation presents
several challenges, such as low n-butanol yield, concentration and productivity, when compared to ethanol biofuel. However, recent research
has been focused on enhancing such issues by developing improved
microorganisms, fermentation techniques and low-energy recovery
methods, in order to reduce production costs.
A good strategy to prove the bio-butanol production technology at
commercial scale is to target the chemicals market, which offers higher
margins and a broad range of applications (Figure 2). Later, consideration could be given to entering the fuels market, which offers far
higher volumes, but lower margins. n
and models presented are prepared on the basis of publicly available and
non-confidential information. The content represents the opinions of Intratec only.
More information about the methodology for preparing analysis can be found,
CW
15
Filtrate
6
Enzyme
Ammonia
CW
17
Residues
14
Lignin
16
CW
CW
ST
EE
CW
CW
Ethanol
Acetone
9
5%
CW
Sulfuric acid
ST
20%
FIGURE 2. Recent U.S. n-butanol demand
BFW
2
26%
12%
n Solvent
Water
32%
n Exports
10
13
11
12
ST
ST
ST
FIGURE 1. The ABE fermentation production process produces n-butanol
ST
n-Butanol
1) Feed handling
2) Screw-feed reactor
3) Flash vessel
4) Ammonia conditioning
5) Continuous hydrolysis
6) Batch hydrolysis/fermentation
7) Beer well
8) Beer column
9) Acetone column
10) Ethanol column
11) Molecular sieve unit
12) Decanter
13) n-butanol column
14) Pressure filter
15) Wastewater treatment unit
16) Energy cogeneration unit
17) Cooling tower
BFW boiler feed water
CW cooling water
EE electricity
ST steam
Sugar Inversion
he substance known colloquially as table sugar is actually sucrose, a disaccharide composed of fructose and glucose. Sucrose
n inis a major agriculturally derived product with an established
dustry for its extraction, processing and supply. It is mainly employed
as
n
a sweetener in industrial and domestic food applications, but also
n finds
additional uses in the pharmaceutical industry, in chemical manufacturn
ing, and as a feedstock for fermentation processes. For example, sugar
n
is used as a feedstock for the manufacture of bio-based chemicals, such
n
as bio-succinic acid.
n
Sugar generally exists commercially as a solid granular product.
However, some food manufacturers prefer to use sugar in a liquid
n form,
due to the ease of handling a liquid product. One commercially available liquid-sugar product is liquid invert sugar, also known as invert
syrup. It is produced from the inversion of sucrose, which refers to the
hydrolysis of the disaccharide molecule into its constituent parts, the
monosaccharides glucose and fructose. The result of this reaction is a
product with greater sweetening power and improved microbiological
stability, when compared to sucrose.
Invert syrups are commercialized with different combinations of invert
sugar and sucrose contents, depending on the degree of inversion performed. Also, invert syrups can be produced by three different inversion
processes: acid hydrolysis with mineral acids; enzymatic hydrolysis; or
hydrolysis by cation ion-exchange resin. The latter process is described
in this column.
The process
The process for sucrose inversion by ion-exchange resin shown in
Figure 1 is similar to the one presented in U.S. Patent 8,404,109, published by European Sugar Holdings S.a.r.l. (Capellen, Luxembourg). An
important feature of this process is the removal of ash from the solution
in the ion-exchange columns.
Sucrose dissolution. Water and steam are mixed to form a hot water
stream. Part of this stream is added to raw sugar (sucrose) before it is
fed to a screw conveyor, which directs wet sucrose to an agitated vessel. The remaining hot water is fed into the vessel, forming a 60 wt.%
sucrose solution.
Sucrose inversion. The sucrose solution is fed to a cation-exchange
column, where some ash is retained and the pH is lowered, allowing
the inversion reaction to occur. Then, part of the inverted solution is fed
to an anion-exchange column, where some ash is removed and the pH
of the solution is increased. Finally, the fully inverted solution is concentrated to 70 wt.% dry matter, forming the final product.
Economic evaluation
An economic evaluation of the sugar-inversion process was conducted,
taking the following assumptions into consideration:
A facility producing 585,000 ton/yr of invert syrup from raw sugar.
The facility was assumed to be located on the U.S. Gulf Coast in the
same location as a plant operating a fermentative process that uses
invert syrup as feedstock
A raw-sugar warehouse with storage capacity equal to 20 days of
operation
Utilities facilities and product storage were not considered in the
analysis
H2O
Raw Sugar
n United States
5%
n Brazil
22%
n India
15%
n European Union
n China
n Thailand
n Mexico
n Others
9%
8%
6%
4%
31%
FIGURE 2. World sugar production by country or region in 2013
The estimated total fixed investment for building such a plant is about
$40 million.
Global perspective
Sucrose can be produced either from sugarcane or sugarbeet plants,
depending on climate conditions. Sugarcane is cultivated in tropical
and subtropical regions, while sugarbeets are more suitable in temperate zones.
In 2013, world sugar production was about 177 million tons (in raw
sugar equivalent). About 80% of global sugar production is derived
from sugarcane, and about 20% is from sugarbeets.
Brazil, the worlds largest sugar producer, accounts for about 22%
of global sugar production, with all of its sugar production originating
from sugarcane.
The worlds main sugar producers are shown in Figure 2. The U.S. is
the only country among them that produces sugar from both sugarcane
and sugarbeet in significant amounts. As the worlds sixth-largest sugar
producer, the U.S. produces 56% of its sugar from sugarbeets, while
the remaining 44% comes from sugarcane. n
and models presented are prepared on the basis of publicly available and
non-confidential information. The content represents the opinions of Intratec only.
More information about the methodology for preparing analysis can be found,
ST
CW
To waste
treatment
5
ST
2
FIGURE 1. The sugar-inversion process shown here uses ion-exchange resins
CW
Liquid
invert
sugar
1) Screw conveyor
2) Dissolution vessel
3) Cation exchange resin bed
4) Anion exchange resin bed
5) Evaporator
CW Cooling water
ST Steam
Technology Profile
Green Ethylene Production
ith a global nominal capacity of about 140 million

ton/yr, ethylene is among
the main petrochemicals
produced worldwide, and is a key
building block for the industry. Ethylene is produced mostly via steamcracking of petroleum-based feedstocks, such as naphtha. Ethylene is
a raw material for the manufacture of
polyethylene, polyvinyl chloride (PVC),
ethylene oxide and other products.
Global concerns about sustainability
and global warming have prompted
the chemical industry to develop production routes for ethylene that utilize
non-petroleum resources. Renewable
ethylene-production alternatives have
begun to emerge in this context.
Green ethylene can be produced
by the dehydration of ethanol, which
can be produced from renewable feedstocks such as sugarcane and corn.
Ethanol-derived ethylene is chemically identical to traditional ethylene, so
downstream processing is equivalent.
next reactor. This is repeated until the

fourth reactor, where ethanol reaches
99% conversion. Next, the reactorproduct stream is cooled in a wasteheat boiler, generating steam.
Quenching, compression, caustic
washing and drying. After reaction,
the product streams water content
is reduced in a quench column. The
ethylene stream leaves by the overheads and is compressed before
entering the washing column, where
impurities are removed with a caustic
solution. Process water is also supplied to this column to avoid caustic
entrainment along with the ethylene
overhead stream, which is cooled by
interchange with the ethylene product stream. Water separated in the
compression and cooling stages is
recycled to the quench column. Next,
the gas stream is dehydrated in a molecular sieve unit.
Purification. After cooling by interchange with the ethylene product, the
dehydrated stream is fed into the ethylene column, where heavy residues
are removed. Next, light impurities are
removed in the stripper column. The
two columns share a single condenser,
which uses propylene refrigerant. The
polymer-grade ethylene (99.9 wt.%)
product is obtained in the bottoms of
the stripper column and used to cool
process streams in heat integrations.
The process
A process for ethylene production
via ethanol dehydration similar to the
processes developed by Chematur
Technologies AB (Karlskoga, Sweden; www.chematur.se) and Petron
Scientech Inc. (Princeton, N.J.; www.
petronscientech.com) is depicted in
Figure 1. The reaction occurs in four
fixed-catalyst-bed adiabatic reactors.
Reaction. Ethanol is vaporized,
heated in a furnace and fed to the
first reactor. During reaction, the temperature drops and the output stream
must be re-heated before entering the
Coast, partially integrated with a

polyethylene complex
Storage capacity equal to 20 days
of operation for ethanol and no
storage for ethylene
The estimated capital expenses (total fixed investment, working capital
and initial expenses) to construct the
plant are about $260 million, while the
operating expenses are estimated at
about $1,400/ton of green ethylene.
Global perspective
An economic evaluation of the process assumes the following:
A facility capable of producing
300,000 ton/yr of green ethylene constructed on the U.S. Gulf
Editors Note: The content for this column is supplied by Intratec

Solutions LLC (Houston; www.intratec.us) and edited by Chemical
Engineering. The analyses and models presented are prepared on the
basis of publicly available and non-confidential information. The content
represents the opinions of Intratec only. More information about the
methodology for preparing analysis can be found, along with terms of
use, at www.intratec.us/che.
C2=
1
Lights
to fuel
ST
FIGURE 2. Operating expenses for green ethylene
The cost of manufacturing ethylene

from ethanol dehydration is highly
dependent on raw material cost (Figure 2). Because ethanol is used as a
biofuel and the crop feedstocks used
in its production are also part of the
food market, ethanol prices may vary
according to the market dynamics of
both food and biofuels.
However, a niche consumer market
may pay higher prices to obtain environmentally friendly products. Therefore, it is possible to commercialize
green ethylene at a premium price,
sufficient to offset the higher production costs of green ethylene.
n
RF
Ethanol
n Net raw materials

cost
89%
n Main utilities
consumptions 6%
n Fixed costs
5%
CW
10
RF
11
ST
12
C2=
PW
2
5
CW
FU
BFW
Caustic
soda
4
CW
To waste
treatment
To waste
treatment
ST
ST
Heavies
to fuel
Ethylene product
(C2=) to heat
integrations
1) Ethanol vaporizer
2) Furnace
3) Reactors
4) Quench column
5) Compression system
6) Caustic washing column
8) Ethylene column
9) Stripper column
10) Cooling tower
11) Refrigerant system
12) Steam boiler
C2= Ethylene product
CW Cooling water
FU Fuel
PW Process water
RF Refrigerant
ST Steam
FIGURE 1. Green ethylene production via an ethanol dehydration process that is similar to Chematur and Petron processes
CHEMICAL ENGINEERING
WWW.CHEMENGONLINE.COM
FEBRUARY 2015
39
Technology Profile
Propane Dehydrogenation: Oxydehydrogenation
ropylene is a major component of the global olefins market and is widely used as an
intermediate for an array of
chemical and plastic products.
Propylene is produced as a byproduct in steam crackers and through
fluid catalytic cracking (FCC) processes. However, due to the increased
availability of inexpensive ethane from
shale gas, ethane has been preferentially used as a feedstock in steam
crackers over naphtha, a practice that
results in minor propylene production.
In this context, on-purpose propylene production routes are of great
interest to the petrochemical marketplace. Among them, propane dehydrogenation (PDH) technology is an attractive option, and has been applied
in several plants around the world.
The process
The PDH process depicted in Figure
1 is similar to the STAR (steam active
reforming) process (Uhde GmbH; Dortmand, Germany; now ThyssenKrupp
Industrial Solutions; www.thyssenkrupp.com), which applies the oxydehydrogenation principle. Two other PDH
processes were previously discussed
in this column (Chem. Eng., Feb. 2013,
p. 33 and Jan. 2014, p. 27).
The STAR process was the first to
apply the oxydehydrogenation principle
for propylene production, significantly
enhancing performance. In this technology, O2 is added to the system to
react with H2, forming water. This reaction lowers H2 partial pressure, shifting
the equilibrium to higher conversion of
propane into propylene while providing
Conversion propane (%)
55
50
45
40
35
Without oxygen
02/HC ratio = 0.05
02/HC ratio = 0.1
30
25
20
550
560
570
580
Temperature (oC)
An economic evaluation of a PDH plant
was conducted, assuming a facility
with a nominal capacity of 450,000
ton/yr of PG propylene erected at a
petrochemical complex on the U.S.
Gulf Coast (no storage for feedstock
and product was considered).
Estimated capital expenses (total
fixed investment, working capital and
initial expenses) for such a plant are
$400 million and estimated operating
expenses are $770/ton of product.n
by Chemical Engineering. The analyses and models presented are prepared on the basis of publicly available and
non-confidential information. The content represents the opinions of Intratec only. More information about the methodology
for preparing analysis can be found, along with terms of use,
at www.intratec.us/che.
Lights
to fuel
RF
14
RF
FU
Lights
to fuel
10
2
CW
CW
PG
propylene
ST
CW
12
CO2
BFW
Propane
RF
6
O2/air
ST
13
ST
ST
BFW
ST
Heavies
to fuel
Water
MDEA Piperazine
make-up make-up make-up
600
from the cold box is sent to the fractionation area, which consists of a deethanizer column for removal of lights
and a propane-propylene (P-P) splitter,
where polymer-grade (PG) propylene is
obtained. Unreacted propane from the
splitter bottoms is recycled.
11
Air
590
FIGURE 2. O2 impact on propane conversion
H2 byproduct
ST
60
the required heat of reaction. Figure 2

shows the effect of O2 addition on propane conversion, according to different
O2-to-propane molar ratios.
Reaction. Propane is fed into a depropanizer column for heavy impurities
removal. The depropanizer distillate is
vaporized, mixed with steam, and preheated before entering the reformer reactor, which is an externally fired tubular reactor where most of the propane
conversion occurs. Next, the reformer
effluent is fed to the oxyreactor, where
H2 is selectively combusted by O2.
The process gas is cooled in a series
of heat exchangers to recover process
heat. Then, it is compressed and sent
to the next area.
CO2 separation. The compressed
gas is fed to an absorption column,
where CO2 is removed in the bottoms
by washing with an aqueous piperazine-activated methyldiethanolamine
(MDEA) solution. The bottoms stream
is depressurized, liberating gases that
are recycled to the absorption column.
The CO2-rich liquid solution from the
flash vessel is fed to the solvent regeneration column, which separates
CO2 in the overheads from the MDEA
solution in the bottoms, which is recycled to the absorption column.
Gas separation. The overhead
stream of the absorption column is
dried in a molecular sieve and fed to
a low-temperature separation system
(cold box) for the removal of lights. In
this system, a H2-rich stream is also
obtained, and is purified in a pressure
swing adsorber (PSA) unit to obtain
high-purity H2 byproduct.
Fractionation. The liquid fraction
ST
1) Depropanizer column
2) Reformer reactor
3) Feed pre-heater
4) Oxyreactor
5) Compression system
6) Absorption column
7) Flash vessel
8) Regeneration column
10) Cold box
11) PSA unit
12) Deethanizer column
13) P-P splitter
14) Refrigeration unit
MDEA Methyl
diethanolamine
CW Cooling water
FU Fuel
ST Steam
FIGURE 1. Propane dehydrogenation process similar to the Uhde (now ThyssenKrupp) STAR process
48
MARCH 2015
Technology Profile
Onsite Enzyme Production
nzymes are proteins synthesized in living cells that act

as biocatalysts for specific
reactions. However, enzymes
must be applied under mild conditions, since they lose their catalytic activity when subjected to heat, organic
solvents or strong acids and bases.
Enzymes are industrially produced
from the fermentation of microorganisms, but they can also be obtained
from plant and animal sources. They
offer high specificity and selectivity
for reactions and substrates, and can
produce enantiopure compounds (in
contrast to chemical syntheses, which
usually produce racemic mixtures).
Enzymes are applied in the production of food, fine chemicals and pharmaceuticals. In addition, they are used
in washing processes, as well as for
a wide range of analytical purposes.
Alternatively, enzyme technology has
been developed to improve sustainable processes that produce existing
products using novel raw materials,
such as biomass.
The process
A typical process for onsite enzyme
production through fermentation is described below, using the enzyme cellulase as an example. Cellulase is used
in the hydrolysis of lignocellulosic material in biomass-based processes, such
as the production of cellulosic ethanol.
Cellulase is industrially produced by a
fungus in an aerobic fermentation in
the presence of a cellulase-production
inducer (Figure 1). The process shown
was compiled from a technical report
published by the National Renewable
1) Medium tank
2) Nutrients tank
3) Pre-fermentation
compressor
4) Pre-fermenters
5) Fermentation
compressor
6) Fermenters
3
Air
Lignocellulosic
biomass
Pretreatment
Nutrients
Fermentation
Distillation
Cellulosic
ethanol
Solid residues
FIGURE 2. A typical cellulosic ethanol production process is shown here
Energy Laboratory (NREL; Golden,

Colo.; www.nrel.gov).
Medium preparation. Glucose feedstock is mixed with water and a small
quantity of cellulase, which converts
part of the glucose to sophorose, a
cellulase-production inducer.
Pre-fermentation. The fermentation
inoculum is prepared in a batch prefermentation step, which occurs in
four trains with three pre-fermenters
each, into which part of the glucose
medium, nutrients and air are fed.
Fermentation. The fermentation step
is conducted in nine fermenters, which
are fed with the fermentation inoculum,
culture medium, nutrients and air. The
fermentation is a fed-batch process, in
which, after the depletion of nutrients
caused by cell growth, glucose medium is fed to the reactors, allowing
continuous enzyme production. After
fermentation, the cellulase-containing
broth can be directly fed to the hydrolysis section of a cellulosic ethanol facility, since the high temperature applied
in this operation is sufficient to inactivate the microorganism.
Economic evaluation
5
CW
Enzymatic
hydrolysis
Air
CW
from Q2 2014. The following assumptions were considered:

A cellulase production unit constructed in the same complex as a
cellulosic ethanol facility located on
the U.S. Gulf Coast
Onsite enzyme production unit manufactures 5,200 ton/yr of cellulase
Storage and utility facilities were not
considered
Total fixed investment for the construction of this unit was estimated at
about $40 million.
Global perspective
Cellulase enzyme is applied to hydrolyze lignocellulosic biomass, which is
used as feedstock in the production
of cellulosic ethanol (Figure 2). In this
way, cellulosic ethanol costs are highly
related to enzyme costs.
Initially, enzyme costs were too high,
so cellulosic ethanol was not costcompetitive with corn-based ethanol.
Currently, many advances in enzyme
technology have been achieved, lowering enzyme costs in cellulosic ethanol by both enzyme production-cost
reduction and enzyme efficiency enhancement. In addition, onsite production allows the manufacture of the
desired enzyme at lower costs, since
some downstream operations present
in a standalone enzyme unit (such as
purification, formulation and storage),
as well as transportation of the enzyme product, are not necessary. n
For more on industrial enzymes, see Tunable Enzymes and the Leaner, Greener CPI in the January
2015 issue of Chem. Eng. at www.chemengonline.com
CW Cooling water
Glucose
water
Cellulase
1
Cellulase
Cellulase
broth
Editors Note: The content for this column is supplied by Intratec Solutions LLC (Houston; www.intratec.us) and edited by
Chemical Engineering. The analyses and models presented are
prepared on the basis of publicly available and non-confidential
information. The content represents the opinions of Intratec only.
More information about the methodology for preparing analysis
can be found, along with terms of use, at www.intratec.us/che.
FIGURE 1. The process diagram shows onsite cellulase enzyme production

36
APRIL 2015
Technology Profile
Hydrogen Production from Natural Gas
ydrogen (H2) is an important

chemical feedstock, mainly
applied in the manufacture
of ammonia and methanol,
and for hydroprocessing operations in
petroleum refineries. Also, since H2 is
an energy carrier, it has been considered for stationary power and transportation applications.
Hydrogen production technologies are separated into three main
categories: thermal, electrolytic and
photolytic. In thermal processes, such
as reforming and gasification, H2 is
produced from biomass and fossil fuels, such as coal and natural gas. In
electrolytic processes, H2 is obtained
from water-splitting, using electricity
that can be generated from a variety
of sources, such as wind. In photolytic
processes, light energy allows hydrogen production using novel photoelectrochemical and photobiological
water-splitting processes.
In the U.S., H2 is mostly produced
from natural gas using the thermal
steam methane reforming (SMR)
process. Natural gas is an important
feedstock for H2 production since it is
widely available and presents a high
hydrogen-to-carbon ratio, reducing the generation of carbon dioxide
(CO2) byproduct.
The process
In the process described below and
depicted in Figure 1, H2 is produced
from natural gas using an SMR process. The process was compiled
based on information available in the
chemical literature.
Sulfur removal. Natural gas feed-
Natural
gas
H2
Central
facility
Distributed
facility
FIGURE 2. There are three types of hydrogen production facilities, and they differ in location and scale of
production
stock is purified by catalytic treatment

with H2 for removal of sulfur impurities.
In the hydrotreater, H2 reacts, over a
catalyst, with sulfur compounds present in the feed stream to form hydrogen sulfide (H2S), which is then adsorbed in the desulfurizer.
Steam reforming. Purified natural
gas is mixed with high-temperature
steam and reformed into CO and H2.
The reforming reaction requires a large
amount of heat and takes place in an
externally fired tubular reactor filled
with catalyst.
Water-gas shift. CO and steam react
in a catalytic water-gas shift reaction,
forming additional H2 and CO2.
Purification. CO2 and other impurities
are removed from the H2 stream in a
pressure-swing adsorption (PSA) system. The purge stream from the PSA
system is recycled to the reformer,
where it is burned with fuel to provide
heat to the reaction. The H2 product
obtained has purities of 99.99 wt.%.
Economic evaluation
An economic evaluation of the process was conducted based on the
following assumptions:
1) Hydrotreater
2) Desulfurizer
3) Reformer reactor
4) Water-gas shift
reactor
5) Pressure-swing
adsorber system
Air
FU
BFW
ST
4
ST Steam
FU Fuel
3
H2
product
5
FIGURE 1. Steam methane reforming process for hydrogen production

48
Semi-central
facility
Hydrogen
point of
use
ST
40160 km
80480 km
A central facility with a nominal

capacity of 450,000 ton/yr of H2
erected on the U.S. Gulf Coast
Distribution costs and storage for
feedstock and product were not
considered
The estimated total fixed investment for the construction of this plant
is about $460 million.
Global perspective
There are three kinds of facilities for H2
production: central, semi-central and
distributed facilities (Figure 2). They
differ in their location and scale of production, characteristics that directly
affect H2 cost, competitiveness and
timeframe to market.
Central facilities are located far from
the H2 point of use and are able to produce large amounts of H2, benefiting
from economies of scale. This type of
facility requires high capital investment,
as well as a distribution infrastructure
able to cover large distances.
Semi-central facilities present intermediate H2-production capacity. They present reduced distribution costs, since they
are sited closer to H2 points of use.
Distributed facilities are small facilities located close to or at the point
of H2 use, reducing delivery costs.
These facilities may present production capacities fitted to local demand.
They require less investment than the
other facilities, although unit production costs may be higher.
n
Editors Note: The content for this column is supplied by Intratec Solutions LLC (Houston; www.intratec.us) and edited by
Chemical Engineering. The analyses and models presented are
prepared on the basis of publicly available and non-confidential
information. The content represents the opinions of Intratec only.
More information about the methodology for preparing analysis
can be found, along with terms of use, at www.intratec.us/che.
MAY 2015
Technology Profile
Bio-based Methionine via Fermentation of Glucose
ethionine is an essential
amino acid that is not produced by animals. Methionine must be obtained
from dietary sources, and its major
use is as an animal nutritional-feed
additive. Methionine is mainly derived
from petrochemical sources. However,
biochemical routes to obtain it have
been researched. For instance, a joint
venture between CJ Bio (cjbio.net) and
Arkema (arkema.com) initiated methionine production using both renewable
and petrochemical raw materials; and
Metabolic Explorer (metabolic-explorer.com), in partnership with Roquette
(roquette.com), developed a process
for 100% bio-based methionine.
cess, which is divided into two phases: batch and fed-batch. Fermenters
are filled with the batch medium, and
fermentation occurs until glucose exhaustion, when the fed-batch phase is
started by adding the fed-batch medium until the end of the fermentation.
Clarification and demineralization.
Culture broth is clarified by the removal of insoluble and soluble organic
impurities by centrifugation and ultrafiltration, respectively. Next, the broth
is demineralized using ion-exchange
resins to remove cations and anions.
Pre-concentration, crystallization
and filtration. L-methionine is concentrated in an evaporator prior to
crystallization under vacuum by water
evaporation. Then, precipitated methionine is sent to a vacuum filter, where
it is separated from the crystallization
mother liquor, which still contains dissolved methionine.
Products recovery. Filtered L-methionine is directed to a dryer, where Lmethionine powder with 99.5 wt.% of
dry matter (90 wt.% of methionine) is
obtained. Evaporated water is sent to
a wash column before being used in
methionine washing during filtration.
Also, the crystallization mother liquor
is acidified with HCl, then concentrated, resulting in the liquid L-methionine
byproduct, which contains 60 wt.% of
dry matter (22 wt.% of methionine).
The process
The production of L-methionine via a
method similar to the one proposed in
patents issued to Metabolic Explorer
and Roquette is described below and
presented in Figure 1. In this process,
L-methionine is produced through a
fed-batch aerobic fermentation, using glucose as the carbon source and
ammonium thiosulfate as the nitrogen
and sulfur source. Products obtained
from this process are L-methionine
powder (final product) and liquid Lmethionine compound (byproduct).
Media preparation. Culture media
used in the fermentation are prepared
by mixing water, corn syrup (70 wt.%
glucose) and aqueous ammonium
thiosulfate solution in medium vessels.
Fermentation. A recombinant microorganism produces L-methionine
through an aerobic fermentation pro-
from Q1 2014. The following assumptions were taken into consideration:
Water
purge
Corn syrup
H20
Ammonium
thiosulfate
solution
A facility erected on the U.S. Gulf

Coast with a nominal capacity of
87,600 ton/yr of L-methionine powder and 86,700 ton/yr of liquid
Storage autonomy of 15 d for feedstock and 20 d for products
Estimated capital investment (total
initial expenses) is about $430 million,
and operating expenses are about
$3,900/ton of L-methionine powder.
Global perspective
Historical methionine-consumption is
presented in Figure 2. Globally, Western Europe, North America and North
Asia are the major consumer regions.
While most regions had similar growth
in methionine consumption (average
growth rates around 5%/yr), North Asia
stands out at 11%/yr. n
are prepared on the basis of publicly available and nonconfidential information. The content represents the opinions
of Intratec only. More information about the methodology for
preparing analysis can be found, along with terms of use, at
www.intratec.us/che.
CW
To flare
H20
3
CW
Air
ST
11
9
6
2
Insoluble
impurities
Soluble
impurities
10
CW
Water
purge
ST
HCI
L-methionine
powder
12
L-methionine
liquid compound
FIGURE 1. Bio-based methionine production via the direct fermentation of glucose

34
FIGURE 2. Methionine consumption by region
CW
5
Corn syrup
H20
Ammonium
thiosulfate
solution
n Africa n Central & South America n Middle

East n North Asia n North America n South Asia &
Oceania n West Europe
1,000
900
800
700
600
500
400
300
200
100
0
2010
2011
2012
2013
CW
13
ST
14
1) Batch medium vessels

2) Fed-batch medium
vessels
3) Fermenters
4) Broth centrifuges
5) Ultrafiltration unit
6) Ion-exchange unit
7) Evaporator
8) Vacuum crystallizer
9) Vacuum filter
10) Vacuum dryer
11) Vacuum wash column
12) Liquid methionine
concentrator
13) Cooling tower
14) Steam boiler
CW Cooling water
ST Steam
JUNE 2015
Technology Profile
Green FDCA Production
oncerns over limited supplies of petroleum-based

feedstocks, coupled with
the global issue of climate
change, have increased demand from
consumers and companies for more
sustainable products. In this economic
environment, chemical and polymer
production from renewable resources
is increasingly viewed as an attractive
area for investment.
Following this global trend, research
on the production of 2,5-furandicarboxyllic acid (FDCA) has intensified
over the last few years. FDCA has
the potential to replace fossil-based
purified terephthalic acid (PTA) in the
production of polyesters and other
polymers containing an aromatic ring.
The most promising application segment for FDCA is for the production
of polyethylene furanoate (PEF). This
polymer exhibits physical properties
and applications similar to polyethylene
terephthalate (PET), and is produced
by the use of FDCA, instead of PTA, in
the PET-production process.
Production process
Figure 1 depicts an FDCA production
process from a glucose solution via the
furan pathway in a process similar to
that developed by Avantium Technologies B.V. (Amsterdam, the Netherlands;
www.avantium.com). This process can
be divided into three main areas: furans
production, methoxy methyl furan (MMF)
purification, and FDCA production.
Furans production. The glucose content of the feed is first enzymatically
isomerized to fructose, and the effluent
Glucose
syrup
is passed through ion-exchange resins

to separate unreacted glucose from
the fructose. The former is recycled to
the isomerization reactor and the latter
is sent to the furans conversion reactor. In the furans conversion reactor,
crystallized fructose is solubilized with
a 95 wt.% methanol aqueous solution
and sulfuric acid. The reaction is conducted at 50 bars and 200C. Fructose is dehydrated to hydroxyl methyl
furan (HMF) and, due to the excess of
methanol, most HMF is converted to
MMF, which is more stable than HMF.
MMF purification. The reactor effluent
is then sent to a distillation system to
recover the solvent and separate the
MMF from other impurities. Methanol
and water are recovered and returned
to the furans conversion area, while
methyl levulinate is recovered as a byproduct. Also, a heavies stream is recovered to be used as boiler fuel, and
finally, purified MMF is recovered and
directed to the FDCA production area.
FDCA production. Purified MMF is
mixed with acetic acid solvent and
a catalyst in the oxidation reactor to
be converted to FDCA. This stream is
filtered to recover crude FDCA. The
acetic-acid-rich liquid is purified using two distillation columns. Catalyst
is also recovered, but it must be reactivated before being recycled to the
process. Crude FDCA is mixed with
water and hydrogen in a hydrogenation reactor, where impurities are removed. The effluent from the reactor
is crystallized, and purified FDCA is recovered from the solid materials. The
liquid effluent is a waste stream.
Global perspective
The main production cost, as in many
commodities-production processes,
is the purchase of raw materials. Not
only is glucose syrup an expensive
source of glucose for this process,
but also the conversion of fructose to
MMF is relatively low, increasing the
raw-material consumption. It would
be beneficial for the profitability of the
process to integrate it with biomass
treatment, in order to obtain raw materials at lower costs. This process
could easily integrate with a biorefinery, where it is possible to achieve a
more efficient valorization of the biomass used as feedstock.
n
Catalyst Acetic acid
Waste water
An economic evaluation of an FDCA
plant was conducted, assuming a
facility with a nominal capacity of
300,000 ton/yr of purified FDCA constructed on the U.S. Gulf Coast. Included was a storage capacity equal
to 20 days of operation for feedstocks
and products.
initial expenses) to construct the plant
are about $600 million, while the operating expenses are estimated at about
$1,550/ton of purified FDCA.
ST
Waste water
2
CW
7
4
Methanol
6
Methanol sol.
Sulfuric acid
CW
CW
14
CW
ST
Water for
recycle
ML
ST
CW
13
CW
ST
Waste water
10
CW
Recovered
catalyst
11
9
12
Water
Hydrogen
ST
ST
ST
ST
Heavies to boiler
Purified FDCA
CW
15
ST
16
1) Isomerization reactor
2) Evaporator
3) Ion exchanger
4) Crystallizers
5) Furan conversion reactor
6) MMF recovery system
7) Oxidation reactor
8) Rotary filter
9) Hydrogenation reactor
10) Crystallizers
11) Centrifuges
12) Rotating dryers
13) Water removal column
14) Acetic-acid-recovery column
15) Cooling tower
16) Steam boiler
ML Methyl levulinate byproduct
CW Cooling water
ST Steam
FIGURE 1. FDCA production process via furans pathway similar to Avantium YXY process
JULY 2015
33
Technology Profile
Lactic Acid Production via Glucose Fermentation
Recovery. The fermentation broth is

decanted and concentrated solids are
filtered, removing mostly biomass. The
aqueous solutions from the decanter
and from the filter are acidified with
sulfuric acid to convert calcium lactate
into soluble lactic acid and CaSO4,
which precipitates. The slurry outlet
stream from the acidification vessel is
fed to a belt filter for solids removal.
The resulting aqueous filtrate is concentrated in an evaporator, then fed to
ion-exchange columns for purification.
Purification. Concentrated lactic acid
is sent to a solvent-extraction system.
First, it is contacted with an organic extractant solution, forming two phases:
a lactic-acid-rich organic phase and
an aqueous phase containing most of
the contaminants. The organic phase
is then washed with water to remove
contaminants. Next, it is contacted
with water at 80C to transfer the lactic
acid into the aqueous phase.The resulting organic phase is washed with
an NaOH solution and then with water to recover the extractant solution,
while the lactic-acid-rich aqueous solution is sent to an evaporator.The concentrated lactic acid stream is fed to a
distillation system where light ends are
removed. Heavy ends are hydrolyzed
and recycled to the process. Lactic
acid is recovered as a side stream.
actic acid is a naturally occurring chiral acid most commonly

found in the L(+) form. Driven
by a recent demand for more
sustainable products, the lactic acid
market has expanded beyond the
food, pharmaceutical and cosmetics
industries. Currently, a major growth
application is for the production of
polylactic acid (PLA) polymer. This biodegradable polymer has the potential
to replace petrochemical-based plastics in applications such as packaging,
paper coating, fibers, films and a wide
range of molded plastic items.
The process
Figure 1 depicts a process for lactic
acid production via glucose fermentation similar to that developed by
Purac (now Corbion; Amsterdam, the
Netherlands; www.corbion.com). This
process generates an 88 wt.% lactic acid solution in water that can be
used as the raw material in polymerization processes. Rigorous control of
fermentation conditions and additional
purification steps are necessary to ensure both optically and chemically pure
lactic acid. The quality of the PLA produced from it depends on the purity.
Fermentation. Glucose solution is
fed to the fermenter. It undergoes a
continuous anaerobic bacterial fermentation, and is converted to lactic
acid. The fermentation temperature is
controlled by circulating cooling water
through internal coils, and the pH is
controlled by the addition of CaCO3
solution, which reacts with lactic acid
to form calcium lactate.
An economic evaluation for a lacticacid production plant was conducted,
assuming a facility with a nominal capacity of 100,000 ton/yr of lactic acid
solution (88 wt.%) constructed on the
Sodium hydroxide solution

Sulfuric acid
ST
CW
Calcium
carbonate
1
Biomass
ST
Extractant
solution
3
CW
Calcium
sulfate
10
ST
ST
Waste stream
13%
11%
n Raw materials
n Calcium sulfate disposal
n Utilities
n Fixed costs
n Depreciation
FIGURE 2. Production costs breakdown
U.S. Gulf Coast, and including storage

capacity equal to 20 days of operation
for feedstock (no product storage). Estimated capital expenses to construct
the plant are ~$200 million, while operating expenses are estimated at
~$1,300/ton of lactic acid solution.
Global perspective
Major production-cost components for
this process are raw material acquisition (mainly glucose and CaCO3) and
CaSO4 byproduct disposal (Figure 2).
Recent improvement efforts focus on
using less costly cellulosic material
to obtain fermentable sugars, and on
developing low-pH-tolerant bacteria
strains, which would decrease both
CaCO3 use and CaSO4 generation. n
Lactic
acid
11
46%
13%
1. Fermenter
2. Decanter
3. Acidification vessel
4. Rotary filter
5. Belt filter
6. Evaporator
7. Ion exchange beds
8. Solvent extraction system
9. Evaporator
Waste
10. Light end column
stream
11. Heavy end column
Waste stream
12. Hydrolysis reactor
CW
13. Cooling tower
14. Steam boiler
Process water
Glucose
17%
ST
ST
12
CW Cooling water
ST Steam
CW
13
ST
14
FIGURE 1. A lactic-acid production process from glucose, similar to the Purac process
AUGUST 2015
37
Technology Profile
Production of Polylactic Acid
olylactic acid (PLA) is the biodegradable polymer of lactic

acid, which is produced via
fermentation processes. For
the last five decades, PLA has been
mainly used in biomedical applications. The development of economical production routes and a rising environmental awareness by the general
public have pushed PLA uses to new
markets, including consumer goods
and packaging applications.
High-molecular-weight PLA can be
produced through two main routes:
an indirect route via a lactide intermediate, and a direct polymerization by
polycondensation. The indirect route
is the most common in industry, and
is employed by two of the major PLA
producers: NatureWorks LLC (Minnetonka, Minn.; www.natureworksllc.
com) and Corbion-Purac (Amsterdam,
the Netherlands; www.corbion.com).
In the indirect process, lactic acid
is first oligomerized and depolymerized to produce lactide, a cyclic dimer of lactic acid. Then, through a
ring-opening polymerization, lactide is
converted to polylactic acid.
PLA production process

Figure 1 depicts a process for PLA
production via a ring-opening polymerization process similar to that developed by NatureWorks. This process
can be divided into two main areas:
oligomerization and lactide formation;
and lactide polymerization. In this process, the optical properties of the lactic acid feedstock are preserved in the
polylactic acid.
Oligomerization and lactide formation. Lactic acid is fed to the oliCW
Biomass
Calcium sulfate
Biomass
treatment &
hydrolysis
Glucose
fermentation
to lactic acid
Lactic acid
conversion
to lactide
gomerization reactor, from which

water vapor is removed, condensed
and sent to a waste-treatment system. The resulting oligomer stream
is mixed with catalyst and fed to the
depolymerization reactor, which is a
packed column operating under vacuum. Water, lactic acid and lactide
are removed in the gaseous overhead
stream. Most lactide and some impurities are condensed and sent to
the drying column, where water is
removed from the crude lactide. The
remaining contaminants are removed
in the purification column, leading to a
99.9% pure lactide product.
Lactide polymerization. The polymer-grade lactide undergoes a meltphase polymerization. Molten lactide,
a stabilizer and catalyst are fed to the
polymerization reactor. The polymer
melt is then pumped to a devolatizer
operating under vacuum to remove
unreacted lactide in the gaseous
stream, which is condensed and recycled to the purification column. The
devolatilized melt polymer is extruded,
pelletized and dried, resulting in PLA
as a final product.
An economic evaluation of a PLA plant
was conducted, assuming a facility
with a nominal capacity of 100,000
ton/yr of PLA constructed on the U.S.
Gulf Coast. Storage capacity for the
final product equal to 20 days of operation was assumed, but raw material storage was not included.
Waste stream
Lactide
ring-opening
polymerization
CW
Global perspective
The recent decrease in oil prices has
reduced the production costs for most
fossil-fuel-based polymers, threatening the competitiveness of PLA projects. Efforts to reduce PLA production
costs must be focused on acquisition
of low-cost raw material. An alternative to allow access to less costly raw
material would be the integration of
PLA production with lactic acid production from a renewable feedstock,
such as biomass (Figure 2; Chem.
Eng. August 2015, p. 37).
In an attempt to reach new markets, some companies are researching methods for producing PLA with
enhanced physical properties. These
methods include the production of a
polymer that consists of a mixture of
poly(L-lactic acid) and poly(D-lactic
acid). This polymer exhibits improved
physical properties when compared
to conventional PLA, produced exclusively from L-lactic acid feedstock. n
CW
1
ST
Catalyst
ST
ST
Waste stream
Stabilizer
Catalyst
Waste stream
CW
Polylactic acid
FIGURE 2. PLA is
produced from
lactide rings

$1,900/ton of PLA.
Waste stream
CW
CW
Lactic acid
Solid waste
1. Oligomerization reactor
2. Depolymerization reactor
3. Drying column
4. Purification column
5. Catalyst melting vessel
6. Polymerization reactor
7. Devolatizer
8. Extruder & pelletizer
9. Dryer
10. Cooling tower
11. Steam boiler
Air
CW Cooling water
ST Steam
CW
10
Polylactic acid ST
11
FIGURE 1. The PLA production process occurs via a ring-opening polymerization process similar to that of NatureWorks
44
SEPTEMBER 2015
Technology Profile
Ethylene Glycol Production
onoethylene glycol (MEG),

also known as ethylene
glycol (EG) or simply glycol, is a diol mostly used
for the production of polyester fibers
and polyethylene terephthalate (PET)
resins. It is also used in antifreeze
applications and in pharmaceuticals
and cosmetics. MEG is conventionally produced through the hydrolysis
of ethylene oxide (EO), which itself is
obtained via ethylene oxidation.
The process
Figure 1 depicts MEG production
from ethylene via a process similar to
the OMEGA catalytic process from
Shell Global Solutions (The Hague,
the Netherlands; www.shell.com). In
the described process, MEG is produced via EO, which is manufactured
in an integrated plant utilizing Shell EO
technology. An important feature of
the process is the negligible production of diethylene glycol (DEG) and
triethylene glycol (TEG), which occur
as byproducts in other ethylene glycol
production processes.
Ethylene oxide production. Ethylene
and oxygen are fed to a multi-tubular
reactor, forming EO. This exothermic
reaction, conducted in fixed beds in the
reactor tubes, occurs in the gaseous
phase with the use of a silver catalyst
supported on alumina. Steam is generated by the heat of reaction.
Ethylene oxide recovery. The reactor product stream is fed to the EO
absorber for lights removal by water
quenching. Part of this gaseous overhead stream is recycled to the reactor,
while the other part is sent to a carbon-
FIGURE 2. PLANTS USING SHELL OMEGA TECHNOLOGY

Company
Location
Capacity (1,000 ton/yr)
Lotte Chemical
Daesan, South Korea
400
2008
Petro Rabigh
Rabigh, Saudi Arabia
600
2009
Shell
Jurong Island, Singapore
750
2009
dioxide-removal unit composed of an

absorber and a stripper. In this unit,
CO2 is separated to be used in ethylene carbonate production.
A diluted EO stream removed from
the absorber is fed to the EO stripper,
where it is concentrated and recovered in the overheads. The crude EO
stream is condensed. Residual light
gases are recovered from it and recycled to the reactor. The resulting EO
stream is directed to the next section.
Ethylene glycol production and purification. Ethylene oxide is reacted
with CO2, forming ethylene carbonate, which is then hydrolyzed to form
MEG and CO2. Both reactions are
carried out in the liquid phase using
homogeneous catalysts.
CO2 streams from the reaction steps
are recycled to the ethylene carbonate
reactor. MEG is purified in two distillation columns where water is removed,
leading to the final MEG product. The
catalyst is separated and recycled to
the ethylene carbonate reactors.

$620/ton of MEG.
Global perspective
Shell OMEGA is the first process to
enable ethylene glycol production via
a fully catalytic process. According
to the licenser, the process is able to
achieve EO-to-EG converstion and
selectivity near 100%, leading to production of MEG only.
However, although 40% of worldwide ethylene glycol production is
derived from processes using Shell
technologies, only three plants in the
world use the new Shell OMEGA technology (Figure 2). As can be seen, two
of these plants are located in Asia,
which is the region of the world responsible by the major share of MEG
global consumption. China alone accounts for about 45% of global demand for MEG.
n
from the first quarter of 2015, assuming a facility with a nominal capacity
of 750,000 ton/yr of MEG constructed
on the U.S. Gulf Coast.

CO2
Ethylene
1. Ethylene oxide reactor

2. Ethylene oxide absorber
3. Ethylene oxide stripper
4. Lights removal unit
5. CO2 absorber
6. CO2 stripper
7. Ethylene carbonate
reactors
8. Hydrolysis reactors
9. Water removal column
10. MEG purification column
11. Cooling tower
12. Steam boiler
O2
Steam
CO2 vent
1
7
CW
8
Water
CO2
10
MEG
ST
Waste stream
ST
Start-up year
ST
Ethylene oxide
9
ST
Catalyst recycle
CW
11
ST
12
CW Cooling water
ST Steam
FIGURE 1. Monoethylene glycol (MEG) production, according to a process similiar to the Shell OMEGA process
44
OCTOBER 2015
Technology Profile
Ethylene Production via Cracking of Ethane-Propane
thylene is a critical building

block for the petrochemical industry, and is among
the most produced organic
compounds. It is usually produced in
steam-cracking units from a range of
petroleum-based feedstocks, such as
naphtha, and is used in the manufacture of several major derivatives.
The process
The process shown in Figure 1 is a
steam-cracking process for ethylene
production from an ethane-propane
mixture. The process can be divided
into three main parts: cracking and
quenching; compression and drying;
and separation.
Cracking and quenching. Initially, an
ethane-propane mixture is fed to furnaces in which, under high-severity
conditions, it is cracked, forming ethylene, propylene and other byproducts.
The furnace outlet stream is subsequently fed to a water-based quench,
to prevent further reactions and formation of undesirable byproducts.
From a decanter downstream from
the quench tower, heavies, condensed dilution steam, tar and coke
are removed. Cracked gas from the
quench is then directed to compression and separation.
Compression and drying. The compression of the cracked gas is performed across five stages. After the
third stage of compression, carbon dioxide and sulfur are removed from the
cracked gas by caustic soda and water washes in a caustic scrubber. The
compressed cracked gas is cooled
and subsequently dried by molecular
sieves that remove most of the water.
Separation. The dried cracked gas

is fed to a cold box for the removal
of hydrogen and light hydrocarbons,
while minimizing ethylene losses.
At this point, condensates from the
chilling train are fed to a series of separation columns. In the first column
(demethanizer), methane is obtained
from the top and further used in the
cold box, while the bottom stream is
fed to a second column (deethanizer).
The top of the deethanizer, composed primarily of ethylene and ethane, is fed to an acetylene converter
and then fractionated in the C2-splitter. In this column, lights are removed
from the overheads and recycled to
the compression system, while polymer-grade (PG) ethylene is drawn from
the column as a side stream. Ethane,
from C2-splitter bottoms, is recycled
to the cracking furnaces.
The deethanizer bottom stream is
fed to a depropanizer, which distills
C3 components in the overheads.
This overhead stream is catalytically
hydrotreated for methyl acetylene and
propadiene removal, and then fed to
the C3-splitter. In this column, lights
are removed from the overheads
and recycled to the compressors,
while polymer-grade (PG) propylene
is drawn from the column as a side
stream. Propane from C3-splitter bottoms is recycled to the cracking furnaces. A C4+ stream is obtained from
the depropanizer bottoms.
13%
59%
13%
n Polyethylene
n Ethylene oxide
n Ethylene dichloride
n Ethylbenzene
n Others
FIGURE 2. Ethylene is made into a host of products
of 1,700,000 ton/yr of ethylene constructed on the U.S. Gulf Coast.

are about $2.37 billion, while the operating expenses are estimated at about
$360 per ton of ethylene produced.
Global perspective
With a global nominal capacity of
about 155 million ton/yr, ethylene is
among the major petrochemicals produced worldwide. The major part of
ethylene production is consumed in
the manufacture of polyethylene, but
ethylene is also applied in the production of ethylene oxide, ethylene dichloride and ethylbenzene (Figure 2). n
from the first quarter of 2015, considering a facility with a nominal capacity
3
Dilution
stream
8%
7%
4
1
Lights to
fuel
Ethane/
propane
To waste
treatment
6
2
CW
7
Tar and
coke to
disposal
Water to waste
treatment
PG
ethylene
product
10
Heavies
to fuel
11
C4+ to
fuel
PG
propylene
by-product
CW
1. Furnaces
2. Quench column
3. Compression system
4. Caustic scrubber
5. Drying unit
6. Cold box
7. Demethanizer column
8. Deethanizer column
9. C2-splitter
10. Depropanizer column
11. C3-splitter
12. Cooling tower
CW Cooling water
PG Polymer grade
12
FIGURE 1. This process diagram shows an ethylene-production process via the cracking of an ethane-propane mixture
42
NOVEMBER 2015

DLMethionineCarbonateProcess

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D,L-methionine production via the

ethionine is an essential amino acid

n Total current capacity (2014) = 1,360,000 ton/yr

potassium bicarbonate (KHCO3) solution from

1 ) Hydantoin primary reactor

2 ) Hydantoin secondary reactor

FIGURE 1. D,L-methionine production via carbonate process

10) Vacumm wash column

11) Cooling tower

he organic compound 1,3-butadiene

side stream of the rectifier column, which

olyethylene (PE) is the worlds largestvolume commodity polymer. Along with

From 250,000 to 349,000 ton/yr

From 150,000 to 249,000 ton/yr

At least 350,000 ton/yr

satility for the production of resins with a wide

Storage of products is equal to 20 days

Editors Note: The content for this column is supplied

FIGURE 1. Solution-phase LLDPE production process similar to Nova Chemicals SclairTech

Heat transfer fluid

Bio-based adipic acid

dipic acid is a dicarboxylic acid that

Cell separation. The fermentation broth is

stock, the bio-based process can be a good

Net raw materials cost

Editors Note: The content for this column is supplied

lion, and the operating expenses are about

cooled before being fed into the fermenter.

uccinic acid is an important industrial

Producing Ethanol from

ressing global issues, such as climate

6. Enzymatic hydrolysis reactor

Recovered chemicals condensate

12. Rectifying column

15. Energy cogeneration unit

Ethanol from Sugarcane

thanol is a widely used commodity chemical with several applications, including

FIGURE 1. Traditional ethanol production process from sugarcane

Ethanol from the Direct

Gas cleanup and conditioning. Syngas

Total fixed investment

million gallons of ethanol per year erected

ncreasing global demand for energy and

thylene is arguably the most important

The bottom stream from the ethylene-water

The estimated capital investment (including

Diethyl ether recycle

Ethanol, water and diethyl ether recycle

1) Aldehyde removal column

ydrogen cyanide (HCN) is a chemical

Plant capacity (thousands ton/yr)

and recycled to the reaction section.

operating expenses according to plant capacity is depicted in Figure 2.

Editors Note: The content for this column is

1 ) Reactor waste-heat boiler

3 ) First HCN stripper

10) Cooling tower

BFW Boiler feed water

The vapor stream from the

thylene and propylene are the most

FIGURE 1. Methanol-to-oleins technology similar to UOP/Hydro MTO process

Raw materials costs

$/metric ton of product