Front.
Energy 2013, 7(1): 127–132
DOI 10.1007/s11708-012-0225-7
RESEARCH ARTICLE
Peng ZHENG, Xuan YAO, Wei ZHENG
Design guidelines for urea hydrolysers for ammonia demand
of the SCR DENOX project in coal-fired power plants
© Higher Education Press and Springer-Verlag Berlin Heidelberg 2013
Abstract Ammonia is highly volatile and will present
substantial environmental and operation hazards when
leaking into the air. However, ammonia is the most
common reactant in the DENOX project to eliminate NOx
in the flue gas. The storage and transportation of liquid
ammonia has always been a dilemma of the power plant.
Urea is a perfect substitute source for ammonia in the plant.
Urea hydrolysis technology can easily convert urea into
ammonia with low expense. Presently, there is still no self-
depended mature urea hydrolysis technology for the
DENOX project in China; therefore, this paper proposes
several guidelines to design the urea hydrolyser by
theoretical analysis. Based on theoretical analysis, a
simulation model is built to simulate the chemical reaction
in the urea hydrolyser and is validated by the operational
data of the commercial hydrolyser revealed in the
literature. This paper endeavors to propose suggestions
and guidelines to develop domestically urea hydrolysers in
China.
Keywords urea, hydrolyser, ammonia, selective catalytic
reduction (SCR)
1 Introduction
Since the introduction of the new air quality standards in
2012, China has become the country which has the
toughest laws on environment protection. Coal fired power
plants in China account for nearly 80% of the share in
electricity market, compared with hydro power and solar,
etc. Therefore, the air pollution from coal-fired power
plants is one of the biggest pollution sources in China. The
government has been monitoring the dust and SOx
Received September 4, 2012; accepted November 9, 2012
✉
Peng ZHENG, Xuan YAO ( ), Wei ZHENG
Beijing GUODIAN Longyuan Environmental Engineering Company
Limited, Beijing 100039, China
E-mail: yaox08@mails.tsinghua.edu.cn
pollution in exhaust gas from power plants all over the
country since 2005. To alleviate NOx pollution, according
to the new regulations, the DENOX projects should be
completed before 2015 all over the country.
As the most effective DENOX technology, SCRs are
preferred by power plants for high NOx removal efficiency.
But the SCR process demands that ammonia source be the
primary reactant to eliminate NO and NO2 in fuel gas.
Liquid ammonia is the best choice for plants far away from
cities for its economic performance. But liquid ammonia is
very dangerous since it is flammable and explosive when
leaking into the air. The government has promulgated a
series of tough laws for the utility, storage and transport of
liquid ammonia. For the power plants close to residential
places, it is forbidden to use liquid ammonia. Industrial
aqueous ammonia is rarely used due to its expensive
transport expense as it has low ammonia concentration.
Besides, industrial aqueous ammonia has a high concen-
tration of metal ions which could damage the catalyst of
SCR (selective catalyst reduction). Therefore, urea is
consider to be the appreciate reactant for the DENOX
project compared with liquid ammonia and aqueous
ammonia, especially for the power plants close to
residential places.
For the current SCR projects, urea should be converted
into ammonia before reacting with NOx in the fuel gas.
Hydrolysis and pyrolysis are the common methods to
convert urea into ammonia. Pyrolysis requires high
temperature (650°C) for the decomposition of urea. The
pyrolysis method cost extra energy and expense for power
plants to maintain the high temperature atmosphere.
Compared with pyrolysis, the hydrolysis technology is
much cheaper and more convenient.
The hydrolysis technology for ammonia demand has
been applied in western countries for years. Although
studies on urea hydrolysis reaction had been stared since
1980s in the urea synthesis area, corresponding applied
technology for the DENOX project have rarely been
achieved in China. There is still no independent domestic
hydrolysis technology to satisfy the large ammonia
128 Front. Energy 2013, 7(1): 127–132
demand in China. Based on former academic studies and
literature, this paper proposed several considerations to
design the urea hydrolyser for industry application, hoping
to propose design guidelines for the development of
domestic urea hydrolysers in China.
2 Theoretical analysis
2.1 Reaction pathway
The process and pathway of a urea hydrolyser is shown in
Fig. 1. Urea solution is feed into the hydrolyser as reactant.
Under a certain condition, hydrolysis reaction occurs to
produce ammonia vapor for the ammonia need of other
systems. The outlet of the hydrolyser is a mixture of vapor
of NH3, CO2 and H2O.
Fig. 1 Process and pathway of a urea hydrolyser
The chemical reaction of urea hydrolysis is a reversible
reaction which occurs under certain conditions [1]. It is
usually believed that the hydrolysis reaction can be
regarded as a two step reaction as follows:
NH2 CONH2 þ H2 O ¼ NH2 COONH4 ,
ΔH ¼ – 15:5  kJ=mol,
NH2 COONH4 ¼ 2HN3 þ CO2 , ΔH ¼ 177 kJ=mol: (2)
The first reaction (1) is a slow process for urea to form
ammonium carbamate (NH2COONH4) and is mildly
exothermic, while the second step (2) is strongly
endothermic and very rapid. Excess water in the feed can
prompt the reaction rate of the urea hydrolysis. Therefore,
for the urea solution with a suitable temperature, the
hydrolysis reaction could easily occur. Considering the
excess water in the urea solution, the overall chemical
reaction formula can be depicted as
NH2 CONH2 þ xH2 O ¼ 2HN3 þ CO2 þ ðx – 1ÞH2 O,
ΔH ¼ 161:5 kJ=mol:
As the overall hydrolysis is endothermic, high tempera-
ture is preferred for high reaction rate. In order to provide
the heat for the chemical reaction, heat flux as electricity or
steam can be used as the heating source.
2.2 Process window
According to the study conducted previously, ammonium
carbamate will decompose under certain conditions. Based
on the empirical formula [1], the relationship between
temperature and ammonium carbamate decomposition
pressure is illustrated in Fig. 2.
Fig. 2 NH2COONH4 decomposition condition and recommend
process window
For most SCR applications, as the ammonia generating
plants have a certain distance from the ammonia injecting
grid or vortex blender, the production of hydrolyser should
require a certain pressure to overcome the resistance of the
pipe. Based on the engineering experience, the pressure at
the outlet of the hydrolyser should be no less than 3.0 barg
(1) (gauge). Therefore, the operation pressure of the hydro-
lyser to produce ammonia should be no less than 4.0 bar in
order to avoid extra pressure prompting equipment.
As indicated in Fig. 2, under a certain pressure, there is a
lowest temperature for NH2COONH4 to discompose into
NH3 and CO2. Therefore, the operation temperature of the
process window should exceed the decomposition tem-
perature of NH2COONH4.
Considering the urea synthesis application, 316 L
stainless steel is the most common material for the reactor.
As demonstrated in Fig. 3, the corrosion rate of 316 L steel
in urea-ammonium carbamate solution is greatly affected
by temperature [2]. When the temperature reaches 160°C–
170°C, the corrosion rate rapidly increases. The urea
hydrolysis reaction prefers high temperature because of its
endothermic character. High temperature will increase the
(3) reaction rate and reduce the volume reactor. However, high
 Peng ZHENG et al. Design guidelines for urea hydrolysers for ammonia demand
Fig. 3 Corrosion rate of 316 L stainless steel with temperature
variation
temperature will lead to a high corrosion rate of the metal
vessel.
Therefore, the reaction temperature should be con-
strained to a small range by multi factors. Based on the
above analysis, it is recommended that the hydrolyser
should be operated in the dot zone as indicated in Fig. 2.
2.3 Mass and energy balance
For the hydrolysis reaction, the overall reaction formula
can be expressed as
NH2 CONH2 þ xH2 O ¼ 2NH3 þ CO2 þ ðx – 1ÞH2 O:
With fixed feed urea concentration, it is easy to calculate
the vapor composition in the product mixture. As the
production has a high concentration of steam vapor which
has high latent heat, the low urea concentration in the
reactant will lead to a high energy cost. Figure 4 represents
the production composition when different urea solutions
are used as the reaction feed stock.
As the reactant urea solution is liquid, while the
Fig. 4 Composition of product vapor and consuming heat
129
production is the mixture of NH3, CO2 and steam vapor
which has high latent heat, low urea concentration in the
reactant will lead to high energy cost. As depicted in Fig. 4,
as urea concentration increases in the feed solution, H2O
production in the vapor increases, while ammonia
production decreases. Besides, when low concentration
urea solution is applied as the feed stock, more energy is
consumed to maintain the reaction.
On the other hand, the hydrolysis reaction rate is
proportional to the urea concentration in the buffer liquid
in the reactor. Therefore, if extremely low concentration
urea solution is used as the feed stock, the hydrolyser
volume should increase to fulfill the ammonia demand
compared with the high concentration urea feed. However,
this does not mean high urea concentration is preferred in
the hydrolysis reaction. As discussed in Sect. 2.1, excess
water is also essential for the pathway of hydrolysis
reaction.
Therefore, considering the reaction rate, energy cost and
reaction pathway, it is recommended that the urea solution
with a weight concentration of 30%–60% should be used
for the hydrolyser process to convert urea into ammonia.
2.4 Phase Equilibrium in the hydrolyser
Both the liquid and vapor phase exist in the hydrolyser. As
the vapor composition is related to the feed stock
concentration, the liquid phase in the hydrolyser would
change whenever the operating condition varies.
According to former studies, it is believed that the
second step of the hydrolysis reaction is a rapid process
compared with the first step. After the urea is converted
into ammonia carbamate with excess water, the ammonia
carbamate immediately decomposes into NH3 and CO2
which exist in vapor phase. As discussed in Refs. [3,4], it is
reasonable to assume to buffer liquid in the hydrolyser
contains urea (including urea derivatives), water, soluble
ammonia and soluble CO2. The ammonium carbamate can
be ignored in theoretical analysis, which has also been
confirmed in former studies.
For the two phase mixture in the hydrolyser, Raoult’s
law, Dalton’s Law, Herry’s Law can be applied to solve the
equilibrium of the solution. Fugacity coefficient and
activity coefficient are used to modify the actual liquid
and vapor compared with the ideal mixture.
The total vapor pressure of the solution is the summary
of the partial pressure of each component.
X
p¼ pi ,
where p equals to the overall pressure of the vapor in the
hydrolyser, pi equals to the partial pressure of each
component in the vapor phase.
For the H2O, the partial pressure can be expressed by the
concentration in liquid phase and statured vapor pressure
under certain temperature:
130 Front. Energy 2013, 7(1): 127–132
pi ¼ xi gi Psta ¼ yi fi p,
where xi equals the mole fraction of component in liquid
mixture, γi equals the activity coefficient of each
component in liquid phase, Psta equals the statured pressure
of vapor under certain temperature, yi equals the mole
fraction of component in the mixture vapor, and fi equals
the fugacity coefficient of each component in the vapor
phase.
For ammonia and CO2, as the operating window is
higher than their critical parameters, Herry’s Laws can be
used to describe the solubility in the water.
pi ¼ yi fi p ¼ xi yi Hi ,
where Hi equals Herry coefficient of each component in
liquid phase.
References [5–8] list the empirical formula and para-
meters of each component. With the conclusions that urea
only exists in liquid phase, and the urea does not
incorporate additional ideality of the reaction solution, it
is easy to describe the phase equilibrium in the hydrolyser.
Figure 5 presents the calculation result based on the
above analysis with 40% (mass fraction) urea feed and 6
bar operating pressure. As discussed in Sect. 2.3, the vapor
composition is affected by the feed concentration in
equilibrium state. In order to keep the phase equilibrium
under difference operation conditions, the liquid phase in
the hydrolyser varies greatly as shown in Fig. 5. With
increasing temperature, the liquid is diluted because more
excess water is vaporized. Meanwhile, the urea and
derivatives in the solution increase due to the excess
water loss. The ammonia concentration in the liquid varies
slightly from 2%–4% due to the variation of Herry
coefficient under different temperatures. CO2 concentra-
tion is extremely low while the weight fraction is always
less than 1%.
Fig. 5 Liquid composition in the hydrolyser with 40% urea feed
stock under 6.0 bar
Under different operation conditions, the liquid phase in
the hydrolyser varies to maintain the phase equilibrium.
For the gas phase, the dew point also changes at different
operation pressures. Based on the liquid-vapor equili-
brium, the dew point of the product vapor with different
feed stock and pressure is calculated, the result of which is
exhibited in Fig. 6.
Fig. 6 Dew point of the product vapor under different operation
conditions
During industry application, the product vapor of
hydrolyser should be overheated to avoid the liquid
formation in order to protect the pipeline and equipment.
Once the liquid is formatted in the pipeline, ammonia
carbamate may format due to the low temperature.
Therefore, the pipeline should be operated above the dew
point temperature for safe and reasonable performance. It
is recommended that heat trace either electricity or steam
should be used to maintain the high temperature of
production pipeline. Either electricity or steam heat tracer
is preferred.
As shown in Fig. 6, for high urea concentration feed
stock, the dew point is higher, which also means higher
heat tracer cost due to the high temperature. In addition, the
dew point line is also greatly related to the operating
pressure. Therefore, the reasonable selection of the
operating pressure for the pipeline is a convenient method
to save extra cost by knocking down the heat tracer
temperature.
2.5 Kinetic characters
A few studies have been conducted on the hydrolysis
reaction in the narrow process window. Lots of hydrolysis
studies are patent protected and reveal a paucity of
experimental data. Brooks et al. [9] have studied the
process to convert urea into ammonia from molten urea
with the supply of vapor in the reactor. Macarthur et al.
 Peng ZHENG et al. Design guidelines for urea hydrolysers for ammonia demand 131

[10] have studied the method of controlling the ammonia

production in a vessel using urea solution as the feed stock.
Cooper and Spencer [11] have studied the method to
convert urea into ammonia by blending steam and solids
urea directly under the temperature of 149°C. Lagana [12]
has invented the method to use pressurized reactor vessel
and steam to stripe ammonia and carbon dioxide product
gas, which also utilizes the hydrolysis reaction.
However, almost all of the work cited above is patented.
Since 2009, Sahu et al. [13–18] have published a series of
papers on the kinetic studies of urea hydrolysis reaction,
and revealed a huge amount of experimental data which
can be used to derive the kinetic formula of the hydrolysis.
The rate of the hydrolysis reaction rate can be described
as
dCA
– rA ¼ – ¼ kCAn     equals  to
dt Fig. 7 The kinetic character of urea hydrolysis reaction
lnð – rA Þ ¼ ln ðkÞ þ nln ðCA Þ,
where k is the forward rate constant, while n is the order of 3 Simulation of the hydrolyser
forward reaction; CA equals the solution concentration in Aspen plus is widely accepted in the chemical industry to
the liquid phase. solve complex process unit. In this paper, the hydrolyser is
According to the Arrhenius principle, the temperature simulated by Aspen plus to verify the reliability of the
dependency of forward rate constant can be written as theoretical analysis. On the other hand, industry operation
k ¼ Ae – E=RT , data from a demonstration hydrolyser is obtained to
compare with the simulation result, as shown in Fig. 8.
where E is the activation energy of the chemical reaction,
and R is the ideal gas constant, 8.314 kJ/(kmol$K).
Aoki et al. [19] believe that the order of the forward
reaction is close to 1 and the reaction rate increases with
increasing temperature. They also reveal some experi-
mental data on the urea hydrolysis.
Sahu et al. [13–18] reveal more detailed experimental
data which can be used to validate Aoki’s theory. The
kinetic date for urea hydrolysis in a batch reactor is listed in
Table 1, which is cited from Ref. [14].
As indicated in Table 1, it can be confirmed that the
reaction is one order. Based on literature surveys, the
experimental data can be used to conduct the activation
energy and frequency factor precisely. The data of the
kinetic character of the chemical reaction can be obtained
by linear fitting, the result of which is given in Fig. 7. The
activation energy and frequency factors of the hydrolysis
reaction are 98 kJ/mol and 1.372E10 min–1.
Fig. 8 Comparison of the simulation and industry result of the
hydrolyser (The hydrolyser operating at 6.0 barg with 50 wt% urea
Table 1 Kinetic date for urea hydrolysis in a batch reactor [14] feed)
Temperature/°C k/min–1 n (calculation) n (average) R2
As there is no corresponding model in the Aspen plus for
140 0.0134 0.947 0.947
urea hydrolyser, the special model is built by insertion of
145 0.0198 1.12 0.979
FORTRAN block including kinetic character into Aspen to
150 0.0220 1.11 1 0.970 describe the chemical reaction [17]. The operation data
155 0.0344 1.058 0.893 concerning the demonstration of a hydrolyser utilized in
160 0.035 0.913 0.935 US [3] are used to verify the reliability of the model. The
hydrolyser is operated under the pressure of 6.0 barg with
132 Front. Energy 2013, 7(1): 127–132
the 50 wt% urea feed stock. As shown in Fig. 8, the
simulation result fits well with the plant data which confirm
the reliability of the theoretical analysis in this paper.
4 Conclusions
According to the theoretical analysis and simulation of
hydrolyser, this paper proposed several guidelines to
design the urea hydrolyser for the ammonia demand in
the power plant. The process window of the hydrolyser
including temperature, operation pressure and feed con-
centration is also suggested by the data analysis and the
theoretical calculation. Based on previous studies, the
kinetic character, chemical equilibrium and phase equili-
brium in the hydrolyser is well described and applied to
simulate the real process in one industrial hydrolyser. The
simulation result fits well with industrial operation record
and confirms the reliability of the model in this paper.
These guidelines could be used as the principles to design
domestic urea hydrolysers in China.
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