Assessing Key Parameters in Ammonium
Carbamate Synthesis for “Blue Urea” Production
Peter Styring
UK Centre for Carbon Dioxide Utilisation, Department of
Chemical & Biological Engineering, The University of
Sheffield, Sheffield S1 3JD, United Kingdom.
p.styring@sheffield.ac.uk
Rhodri E Owen
UK Centre for Carbon Dioxide Utilisation, Department of
Chemical & Biological Engineering, The University of
Sheffield, Sheffield S1 3JD, United Kingdom.
Abstract — This paper addresses a major challenge in
urea synthesis. Traditionally this is achieved by the thermal
decomposition of ammonium carbamate under high pressure.
Here we show that urea can be produced by carrying out the
thermal composition under an atmosphere of carbon dioxide
at atmospheric pressure. If the gas atmosphere is changed to
nitrogen, the undesired decomposition to ammonium
bicarbonate occurs as evidenced by 13C NMR. The urea
synthesis becomes less energy intensive and if coupled to
ammonia synthesis using renewable hydrogen, rather than
steam reformation of methane, then the carbon dioxide
emissions associated with the whole process are significantly
reduced.
Keywords—urea, ammonium carbamate, CO2 utilisation, low
carbon, selective
I. INTRODUCTION
Growing concern over climate change due to increased
emissions of carbon dioxide (CO2) and other greenhouse
gases (GHGs), such as methane (CH4) and nitrous oxide
(N2O) with high global warming potential [1] have led to
technologies aiming to abate emissions. CO2 is produced
naturally in large quantities by events such as volcano
activity, and it is also release anthropogenically through the
combustion of large quantities of fossil fuel. Historically,
these emissions have been balanced by the natural carbon
cycle; using huge sinks such as the ocean, terrestrial plants
and land and the atmosphere. However, due increased use
and reliance on fossil fuels [2], more CO2 is released into
the atmosphere than can be accommodated by the natural
carbon cycle. This has caused the CO2 concentration in the
atmosphere to be in excess of about 400 ppm [3,4] with
average annual global warming increasing by around 0.8
o
C. To bring these numbers into perspective, the IPCC [1,5]
predicts that without measures to mitigate GHG emissions,
atmospheric CO2 concentration will be excess of 750 ppm
by 2100 with a temperature rise of 4.8 oC against 1990
levels. Such rises are associated with catastrophic global
events such as melting of ice caps or sheets, rise of sea
Justin G Driver
UK Centre for Carbon Dioxide Utilisation, Department of
Chemical & Biological Engineering, The University of
Sheffield, Sheffield S1 3JD, United Kingdom.
Richmond Godwyll
UK Centre for Carbon Dioxide Utilisation, Department of
Chemical & Biological Engineering, The University of
Sheffield, Sheffield S1 3JD, United Kingdom.
level, draught in certain parts of the world and general
changes in world climates.
The severity of this problem is further exemplified by
the excessive use of fossil fuel especially by emerging
world economies [6]. Although advances are being made to
switch to cleaner energy sources, such as solar and wind
power, it is believed that more time will be needed to
develop these energy technologies to reliable standards and
capacities [7,8]
Drives to reduce CO2 emissions due to the use of fossil
oil has motivated researchers to come up with variety of
potential mitigation technologies. Carbon Capture and
Sequestration (CCS) allows further fossil oil to be used and
the CO2 captured and sent to geological landfill in depleted
oil fields and saline aquifers in particular. Although CCS
with Enhanced Hydrocarbon Recovery (EHR) promises to
store CO2 in identified natural sinks (depleted oil reservoirs,
unmined coal seams and saline aquifers), their sustainability
has still not been well established [1,9] and operation results
in the continued use of more fossil oil with subsequent
GHG emissions. Carbon Capture and Utilisation (CCU) on
the other hand, continues to challenge researchers to
develop processes that utilise CO2 as a feedstock for
chemical syntheses [10,11], avoiding the use of new
petrochemical feedstock. However, CCU is not without its
challenges. Among these are the challenges of increasing
product yields or conversion and energy penalties [12].
Urea is a common chemical fertiliser whose production
consumes the largest global amount of CO2. However, the
conventional industrial synthesis (Scheme 1) operates at
150 bar pressure and 180 - 210 oC temperature [13],
conditions which are high in energy demand. The
possibility to synthesise urea under milder conditions of
pressure (< 14 bar) and temperature (120 - 140 oC) has been
demonstrated by Barzagli et al. [14]. This is a significant
achievement because CO2 utilisation for chemical syntheses
in particular, as reported by Aresta (2010), accounts for
only 10% of the possible offset margin, and the remaining
is associated with fuel (energy) sources. Thus, for instance,
halving the energy penalty associated with any CO2 its bolted end with several layers of plastic paraffin film
utilisation project will increases the actual CO2 offset to (PARAFILM “M” ®); such that the glass tube formed an
about 55%. air-tight shell around the steel pipe to the bolt.
The glass tube was also furnished with a sparger at the
end. This fitting was arrayed with plastic circular baffles
along its length to reduce the impact of the re-circulated
liquid stream on that in the column. To some extent, this
arrangement also helped to increase the residence time of
the reacting gases. The second tube was for the gas exit,
which was connected to a gas scrubber. This was made of a
polyethylene (PE) tubular fitting that connected an opening
through the bung to the reactor column and the NH3
Scheme 1 Synthesis of urea from CO2 scrubber. The remaining two tubes constituted the liquid
recirculation loop. It had a 10 mm steel pipe outlet which
The success of this new green technology on industrial ran almost parallel to the ammonia inlet tube and an intlet
scale, however, will depend very much on process and which was a 10 mm steel tubular fitting that opened to the
design considerations in order to obtain highly pure and absorber column passing through the rubber bung.
relatively stable intermediates (ammonium carbamate) that
can be converted to obtain higher urea conversions with less
energy input. These reasons coupled with decarbonising
existing processes to make them more sustainable. While
the Bosch-Meisner process for urea production is usually
carried out in the gas phase, the high pressures involved
usually mean that the process must be carried out at
elevated pressure. Here we consider the use of a solvent
based process that can be carried out under ambient
pressures. The tern ‘blue’ urea reflects that the ammonia is
produced from ammonia that is produced using renewable
hydrogen, prepared from the electrolysis of water using
renewable energy sources.

II. EXPERIMENTAL METHODS

The main experimental setup is shown in Fig. 1 and
comprised of an absorber, filtration unit, liquid recirculation
pump, gas rotameters, gas valves and a gas scrubber. Care
was taken to ensured that none of the components were
made up of copper metal or it alloy as a precautionary
measure, since NH3 is known to corrode copper.
Cleaned gas out

3-way valve Fig. 2 Schematic of the absorption bubble column

V-5

F-2
reactor
F-1 Flow
meters
Absorption
Column
Filtration Reactor
V-2 V-3 V-4

unit
Peristaltic pump
V-1
NH3 scrubber
CO2
Gas bottles
To product separation weighing
Fig. 1 Schematic of the experimental rig
The Absorption gas bubble reactor used was constructed
from a 40 mm ID x 500 mm long glass column adapted as a
bubble column reactor. This column was already equipped
with a sintered glass disc, gas distributer (sparger) at the
bottom. The top was fitted with a rubber bung which was
perforated with holes to hold four tubes. The first tube, for
the purpose of introducing ammonia into the absorber, was
made to run through the middle of the bung. This was a 5
mm steel pipe fitted tightly to a 10 mm narrow glass tube at
The filtration unit comprised a 50 mm ID x 80 mm long
PET plastic container with holes perforated at both ends
NH3 N2
(top of lid and bottom of container). These holes were fitted
with PE tubular fittings. The outlet of the liquid
recirculation loop was connected with soft rubber tubing to
the top of the filtration unit, whereas the bottom tubular
fitting was connected to the inlet of the liquid recirculation
pump, also by soft rubber tubing. Inside the filtration unit
were placed several layers of filter materials comprising of
(from the bottom up) a 1.5 mm perforated PE plastic
support, 10 mm foam and 2 filter papers; all of which were
cut to fit the inside diameter of the filtration unit.
The liquid recirculation pump was employed to assist
with the removal solid products from the absorber, when
they were formed in order to prolong the equilibrium of the
reaction. The pump used was a Behr laboratory Peristaltic
pump PLP 330 with variable speed settings between 20-100
rpm and maximum flow capacity up to 400 mL/min. Gas
flow rates were accurately measured using SUPELCO
rotameters. The gas rotameters were originally designed for
air, and thus needed to be calibrated for CO2 and NH3
respectively. Throttling gas valves were used to reduce the
inlet gas pressures and needle valves for setting accurate
gas flow rates. With the use of these valves, the inlet
pressure of CO2 and NH3 gases to the absorber were
reduced from the cylinder pressures of 7 - 9 bar to 0.25 bar
and 0.4 bar respectively to ensure that the glass absorber
with its components stayed intact throughout the
experiment without being damaged under excessive gas
pressures.
The gas scrubber served to neutralise any excess NH3
that escaped from the absorption column to prevent its
release into the atmosphere. This was a Drechsel bottle
containing a solution of dilute sulphuric acid and universal
indicator. The scrubber’s inlet section was connected to the
gas exit tube from the bubble reactor by translucent silicone
soft rubber tubing, whereas the scrubber’s exit stream was
extended with another translucent silicone soft rubber
tubing to discharge the exit gas substantially high above the
experimental rig.
The type of filter paper used for the vacuum filtration
was 70 mm Grade 5 Whatman filter paper manufactured by
GE Healthcare Life Sciences.
Carbon dioxide gas (100%) and NH3 (100%), were
contained in gas cylinders and purchased from BOC Gases.
All other chemicals were purchased from Sigma-Aldrich
and used without further purification. The chemicals used
include isopropyl alcohol (propane-2-ol) (IPA) (99.96 –
99.97%) HPLC grade purchased from Sigma Aldrich.
0.25M Sulphuric acid (H2SO4) was prepared from
concentrated acid solution and placed in a Drechsel bottle,
adding few drops of universal indicator to give a pink acidic
solution. The rig was also connected to a nitrogen (N2) gas
tap to supply low back pressure to prevent the IPA from
rising up in some of the tubes by capillary action after
reaction was stopped and also to purge lines or tubes of
NH3 regularly.
Different experimental procedures were used to assess
the effect of factors such as quantity (volume or height) and
recycle rate of reaction liquid medium (IPA), reactants mole
ratio, product seeding, reaction temperature and different
gas contact distances on the rate of ammonium carbamate
formation and on reactants conversion. All experiments
were carried out with a CO2 pressure of 0.25 bar and NH3
pressure of 0.4 bar to the rig by throttling the valves on the
pressure gauges of their respective cylinders or flow stream.
This was done to maintain the integrity of the fittings on the
experimental rig and also to ensure that relatively safe
working conditions are created.
The experiments were conducted in a fume cupboard.
All the experiments were carried out at atmospheric
pressure and at the specified temperature. Unless otherwise
specified, experiments were conducted at a standard gas
contact distance of 20 mm.
The bubble reactor was filled with IPA to approximately
50 mL and the liquid recirculation pump was started,
increasing the speed gradually to the required speed in rpm.
The pump was left to run until a steady recirculation rate
was achieved with an approximate required IPA column
height. Where the required height was not obtained, more
IPA was added to the recirculation loop by topping up via
the filtration unit. When the correct height was reached and
stabilised, CO2 was allowed into the reactor by opening the
needle valve on the CO2 rotameter first, followed by the
opening of the CO2 inlet valve to the column and then
increasing the flow rate to the required value in mL/min.
Next the NH3 was introduced by opening the needle valve
on the NH3 rotameter and gradually increasing it to the
required flow rate in mL/min. Timing commenced
immediately upon reaching the required NH3 flow rate. The
flow set points for both reactants were, after that, monitored
throughout the duration of the reaction. At the end of the
appropriate reaction time, the reaction was stopped by first
turning the NH3 flow off. This is then followed by the
simultaneous closing of the CO2 inlet valve at the bottom of
the reactor and turning off the flow of the CO2.
The CO2 tubing, as well as the bung with the other
tubes, was then disconnected so that the solid products
could be separated together with that collected by the
filtration unit by vacuum filtration in order to obtain the
total yield over the tested duration or reaction time. The
separated solid product was weighed immediately, as it was
found to be unstable under ambient conditions of
temperature and pressure.
At a steady state IPA recycle rate of 100 rpm, fixed
reactants mole ratio (NH3/CO2) of 2.0 comprising of NH3
(100 mL/min) and CO2 (50 mL/min) were reacted to form
product, which was separated by filtration, dried and
weighed immediately. The tests were carried out for an IPA
volume of 100 mL over different reaction times.
Owing to these challenges from the use of the
recirculation loop, the subsequent experiments were
conducted without IPA recirculation.
A. Effect of different IPA volumes without IPA
recirculation
Without recycling the IPA in the absorption column,
fixed reactants mole ratio (NH3/CO2) of 2.0 comprising of
NH3 (100 mL/min) and CO2 (50 mL/min) were reacted over
different reaction times ranging from 10 min to 60 min to
form products. The solid products were separated by
vacuum filtration and weighed immediately. This procedure
was carried out for IPA volumes of 100, 150, 200, 250 and
300 mL.
B. Effect of reactants mole ratios at constant IPA volume
and reaction time
With a constant IPA volume of 200 mL, initial reactants
mole ratio (NH3/CO2) of 1.5 comprising of NH3 (75 - 150
mL/min) and CO2 (50 mL/min) were reacted over 30 min
without recycling the IPA in the reaction column. The
products formed were separated by vacuum filtration and
dry yields determined. The experimental procedure was
repeated for reactant mole ratios of 2.0 [NH3 (100 mL/min)
and CO2 (50 mL/min)], 2.1 [NH3 (105 mL/min) and CO2
(50 mL/min)], 2.2 [NH3 (110 mL/min) and CO2 (50
mL/min)], 2.5 [NH3 (125 mL/min) and CO2 (50 mL/min)]
and 3.0 [NH3 (150 mL/min) and CO2 (50 mL/min)].
C. Effect of product seeding
Different weights (0.5, 1.0, 1.5, 2.0 and 3.0 g) of solid
carbamate placed into the reaction column and then
immediately topped up with IPA to a constant height of 200
mL. Reactants mole ratio (NH3/CO2) of 2.0 comprising of
NH3 (100 mL/min) and CO2 (50 mL/min) were reacted over
10 min without recycling the IPA in the bubble column
reactor. The product formed was separated by vacuum
filtration, dried and weighed immediately.
D. Effect of different reaction temperatures
IPA (210 mL) was chilled and maintained at 0 oC. 200
mL of the IPA was then poured into reaction column. The
column was lagged with a jacket of ice made from a 2.5 L
plastic PET bottle cut opened on both end such that the
smaller end could fit the diameter of the reactor. The
reaction temperature was maintained at 0 oC. Reactants
mole ratio (NH3/CO2) of 2.0 comprising of NH3 (100
mL/min) and CO2 (50 mL/min) were reacted over 60 min
without recycling the IPA in the bubble column reactor.
The product formed was separated by vacuum filtration,
dried and weighed immediately.
E. Effect of different gas contact distances
The gas contact distance is the distance between the two
gas spargers. The design of the bubble column reactor was
such that this distance could only be varied between 20 - 35
mm. The experiment was, therefore, carried out separately
for gas contact distances 20 mm and 35 mm.
With a selected constant IPA volume of 200 mL,
reactants mole ratio (NH3/CO2) of 2.0 comprising of NH3
(100 mL/min) and CO2 (50 mL/min) were reacted over 60
min without recycling the IPA in the reaction column. A
thermometer was retrofitted in place of liquid recirculation
inlet tube to monitor the temperature changes within gas
contact region and the region a 50 mm above it.
F. Determining Product Yield
Solid products were weighed immediately after vacuum
filtration as follows. The cylindrical part of the Buchner
funnel, containing the separated product with filter paper,
was detached and air dried before taking the mass of the
solid.
G. Product Characterisation
Decomposition studies of the ammonium carbamate
product under a variety of gaseous atmospheres and
conditions of pressure and temperature were carried out
using a Hiden Intelligent Gravimetric Analysis (IGA)
system. Carbon-13 Nuclear Magnetic Resonance (13C
NMR) Spectroscopy, was used to determine purity relative
to a reference compound.
III. RESULTS AND DISCUSSION
A. Effect of different IPA volumes at constant IPA
recirculation rate
Parameters were fixed at a recirculation pump velocity
of 100 rpm, IPA volume of 100 mL, NH3/CO2 ratio of 2.0,
ambient temperature of 21oC, pressure 101.325 kPa, and a
gas contact distance of 20 mm. The yield of ammonium
carbamate (ACm) obtained for different reaction times
using IPA volume of 100 mL with IPA recirculation (100
rpm pump velocity) was compared with that for 100 mL
without IPA recirculation. Surprisingly the conversion of
CO2 to ACm was greater (peaking at 72%) witout IPA
recireculation than with circulation (36%).
Recirculation of the reaction liquid medium (IPA)
generated the challenge of dealing with pressure drop in the
filtration unit. However, as the best conversion was
observed without IPA circulation it was decided to not use
recirculation in future studies reported here.
B. Effect of different IPA volumes without IPA
recirculation
Increase in IPA height at constant tube diameter, so
volume, generally resulted in increased conversion of
reactants over reaction times longer than 30 minutes.
However, for such increased IPA heights, the initial rate of
formation of products was relatively slower, observed by
reduced conversion for reaction times below 10 minutes.
The fact that the reaction required more time before it
started for larger IPA volumes suggests that the overall
reaction rate is also influenced by mass transfer rates from
the gas phase into the bulk liquid phase. This mass transfer
rate also depends hugely on the height of the liquid column
and residence time (Bamford et al., 1985). Therefore, the
greater the liquid volume, the longer it will take for gas
molecules to diffuse and saturate the bulk liquid in order for
the reaction to proceed.
C. Effect of reactants mole ratios at constant IPA
height and reaction time
Conversion of CO2 was observed to increase with
increasing reactants mole ratios (NH3/CO2), giving the
highest conversion (75.1%) with regards to the conditions
for the test at an NH3/CO2 ratio of 2.1. Above this, the CO2
conversion was observed to decrease. Significant decrease
in NH3 conversion was observed when the mole ratios were
increased beyond 2.1. This observation, to some extent, is
in line with a similar observation made by Barzagli et al.
(2011), where they reported that, higher CO2 capture
efficiency were obtained for reactions operated in slight
excess of NH3 with an NH3/CO2 ratio of 2.1 – 2.2.
 D. Effect of product seeding at constant IPA volume
and reaction time
The reactor tube was seeded with pure ammonium
carbamate in order to determine if reaction could be
promoted. Conversely, addition of ACm seed crystals
resulted in a decreased conversion for addition of product
from 0.0 – 3.0 g. As this is an equilibrium reaction this
confirms that rather than helping to seed the product from
solution it in fact pushes the equilibrium back to the
reactants.

E. Effect of reaction temperature at constant IPA

height and reaction time
At a reaction temperature lower than standard ambient
temperature (< 21 oC), the reactants conversion was Fig. 3 Temperature profiles during reaction compared
observed to decrease. Conversion was observed to be 66% for in the gas contact region and 50 mm above. Fixed
at 21 C And 57% at 0 C. parameters: NH3/CO2 ratio (2.0), IPA volume (200 mL),
Reaction time (60 min), ambient temperature (21oC),
F. Effect of gas contact distance at constant IPA pressure (101.325 kPa), sparger separation 20 mm.
height and reaction time
A decrease in conversion was observed with increased
distance between the NH3 and CO2 spargers. A conversion
of 69% was observed with a separation of 20 mm. This
decreased to 63% when the separation increased to 35 mm.

G. Temperature change within the reactor

The reactor was started with an initial temperature of 20
o
C and the internal temperature of the reactor was
monitored using a thermocouple at two points: (a) within
the gas contact region and (b) 50 mm above the contact
region. The data are shown in Fig. 3
20 mm and 35 mm gas contact distances. Fixed
parameters: Within experimental error, the temperature rise
is equivalent in both cases which suggests a uniform
reactoion profile across the reactor. This also indicates that Fig. 4 Temperature profiles during reaction compared
the reaction is mildly exothermic with a temperature for 20 mm and 35 mm gas contact distances. Fixed
increase of 7 C over the 60 minute reaction period. The parameters: NH3/CO2 ratio (2.0), IPA volume (200 mL),
reduction in temperature increase in the last 10 minutes of Reaction time (60 min), ambient temperature (21oC),
reaction also suggests that equilibrium is reached after 50 pressure (101.325 kPa), sparger separation 20 mm.
minutes under these conditions.
H. Decomposition of the ammonium carbamate to produce
The temperature was also monitored 50 mm above the
contact region using sparger separations of 20 and 35 mm. urea
The data are shown in Fig.4 and show a slight difference The thermal decomposition of samples of solid
between the two configurations. ammonium carbonate were studied by
thermogravimetrically using an Intelligent Gas Analyser
For the 20 mm sparger separation, there is again an 8 C (IGA) separately under static CO2 and N2 pressures. There
temperature increase with equilibrium conditions being was no buoyancy correction done for the IGA analysis, as
reached after 50 minutes. However, for the 35 mm its effect on the results was deemed insignificant. Fig. 5
separation there is an 8 C temperature rise and the shows the decomposition thermogram of ammonium
temperature rise has stabilised by 60 minutes but is not carbonate under a static 1 bar CO2 pressure. showed two
decreasing significantly. This suggests that the reaction is stages of decomposition starting at 25 oC and completing at
diffusion limited, as suggested previously, and while 50 oC
maximum conversion is not achieved, if the reaction were
to run to higher times then equivalent conversion would be
achieved. We therefore propose that the reaction kinetics
are diffusion limited.

Fig. 5 Two-Step decomposition of solid ammonium
carbamate under static CO2 pressure.
There are three competing reactions for the
decomposition of ammonium carbabmate as shown in Fig.
6: (a) the desired dehydration to give urea (M = 78 Da) and
water (M = 18 Da); (b) deamination to give ammonium
bicarbonate (M = 63 Da) and ammonia (M = 15 Da); (c)
dimerization of urea to give biuret (M = 103 Da) and
ammonia.
Fig. 6 Three thermal decomposition pathways of solid
ammonium carbamate.
The first thermal event occurs at the initial temperature
of 25 C. The starting weight of 50 mg immediately
decreases under a flow of pure CO2 to give a new species
with a mass of 36.5 mg, representing a percentage weight
loss of 23%. If we consider the decomposition pathways in
Fig. 6, then process (a) loses water and represents a
percentage weight loss of 23%; (b) loses ammonia with a
weight loss of 27%; (c) loses one ammonia for two
molecules of ammonium carbamate with a weight loss of
13.5%. If we consider the weight loss in Fig. 5 then this is
consistent with the loss of water to give urea. There is a
very strong correlation to suggest pure urea is formed under
a 1 bar CO2 pressure. This is an improvement on the normal
procedure which requires the atmosphere to be over-
pressured with CO2.
The same process was carried out but replacing 1 bar
CO2 with 1 bar nitrogen, as seen in Fig. 7. It is clear that a
different process is observed. The initial weight loss at
ambient temperature is followed by a second event to give a
product that is stable at 50 C. This intermediate then
decomposes at 80 C with complete weight loss. The initial
weight loss at 50 C to give the intermediate at 103 mg
represents a weight loss of 37 Da (26.5%). This corresponds
to the loss of ammonia in process (b) which has a
theoretical weight loss of 27%. This shows that ammonium
bicarbonate is being formed rather than the desired urea and
shows the importance of performing the decomposition
process in the correct atmosphere.
Fig. 7 Two-Step decomposition of solid ammonium
carbamate under static N2 pressure.
Under ambient conditions of temperature (21 oC) and
pressure (1 bar), a sample of solid ammonium carbamate
placed in the IGA equipment was observed to decompose
rapidly. The rate of decomposition was seen to increase
even more when the sample was subjected to vacuum
pressure (< 1 bar). This characteristic explains why rapid
weight loss was noticed during weighing of solid products,
and it is suspected to have caused losses during vacuum
filtration as well. Therefore, it is recommended that drying
is achieved using a positive pressure of CO2. To achieve
this we are looking to use a Doctor M Fundabac pressure
filtration unit. Indeed, Barzagli et al. [14] reported that their
product was dried at room temperature with a low flow of
CO2 after washing with CO2 saturated solvents in order to
prevent decomposition of the product.
In order to verify the nature of decomposition under
nitrogen, 1 g of the solid product was heated at 50 °C for 4
minutes in an open top Schlenk tube under a constant flow
of nitrogen. The resulting solid was characterised by 13C
NMR (Brueker AVIII) operating at 400 Mz using D2O as
solvent. According to the thermogram in Fig. 7, the solid
should be a mixture formed due to the partial
decomposition of ammonium carbamate. The spectrum is
shown in Fig.8 and shows residual isopropanol (IPA) and
two additional peaks. Unreacted ammonium carbamate is
observed at 166 ppm consistent with the reference
spectrum. The additional peak at 162 ppm is consistent with
the formation of ammonium bicarbonate.
Fig. 8 13C-NMR Spectrum for the product mixture
isolated during the incomplete decomposition of
ammonium carbamate under a nitrogen atmosphere. D2O,
400 MHz: ammonium carbamate δ = 165.6 ppm;
ammonium bicarbonate δ = 162.4 ppm.
IV. CONCLUSIONS
As opposed to the gas phase reaction of NH3 and CO2,
the synthesis of ammonium carbamate by the gas-liquid
method, as demonstrated by this study, provides enough
flexibility to control reaction parameters and factors such
as reaction temperature, gas contacting, reactants
conversions and products separation.
It has also been established from the results of this
study that the volume of IPA (and so liquid height for
constant tube diameter) in the absorber inversely
influenced the rate of the reaction, although in each case
the reaction was fast.
The highest reactants conversion obtained from the
study (85%) was achieved with IPA volume of 300mL,
reactants mole ratio (NH3/CO2) of 2.0, and gas contact
distance of 20 mm under ambient conditions of pressure
(101.325 kPa) and temperature (21 oC). However,
following from the findings made as to how to harness and
exploit these parameters, the highest conversion recorded
may be further increased by using a smaller gas contact
distance (<20 mm), a mole ratio of 2.1 and employing
temperature control measures to maintain the reaction
temperature well below 25 oC.
V. ACKNOWLEDGEMENTS
We are grateful to the Biotechnology and
Biological Sciences Research Council (BBSRC) for
funding to REO under grant BB/M011917/1 and the
Engineering and Physical Sciences Research Council
(EPSRC) for funding a DTA Studentship to JGD and the
CO2Chem Network (EP/K007947/1 & EP/H035702/1).
We also thank The University of Sheffield for funding to
RG.
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