International Journal of Multimedia and Ubiquitous Engineering

Vol.11, No.6 (2016), pp.131-142

http://dx.doi.org/10.14257/ijmue.2016.11.6.12

Development, Application and Direction of Development of Urea-

SCR

Zhanfeng Qi1, Shusen Li1 and Xiuli Guo2

1
Northeast Forestry University, Harbin 150040, China
2
Dalian University, Dalian 116622, China
[email protected]

Abstract
Nitrogen oxide (NOx) is one of main pollution sources of air pollution, so it need to be
more and more stringent emission regulations limiting pollution. Selective catalytic
reduction (SCR) technology is the mainstream technology to remove NOx at euro V and
euro VI stage. By analyzing chemical reaction mechanism of selective catalytic reduction
(Urea-SCR) of urea, research actuality of Urea-SCR from the urea storage device, urea
supply system, catalystic converter and control unit separately was pointed out. At last
development trend of SCR technology based on research that we have was analyzed.

Keywords: Urea-SCR, NOx, Reaction mechanism

1. Introduction
Recently, with the aggravation of global atmospheric pollution and increase of
awareness for environmental protection, the NOx after-treatment technology is paid more
and more attention. NOx after-treatment technology includes the direct catalytic
decomposition technology, selective non-catalytic reduction (SNCR) technology,
selective catalytic reduction (SCR) technology, NOx storage reduction (NSR) technology
and plasma-facilitated catalysis (PFC) system. The promotion of practical applications of
direct catalytic decomposition technique and SNCR are limited in the field of automobile
exhaust purification due to their own limitations. NSR that is also called NSC (NOx
Storage Catalyst) or LNT (Lean NOx Trap Catalyst) is a technology pathway developed
firstly by Toyota in 1996. It is the mainstream technology of light diesel engines to reduce
the NOx, and it is suitable for applications where space is not enough to install SCR
system especially. This technology has few applications in China. There are still some key
theoretical and technical difficulties of PFC technology to be resolved, so this technology
still in the process of theoretical research and experimental studies.
As the mainstream technology of heavy duty diesel engines to reduce the NOx, SCR
refers to the reaction of exhaust and NOx to N2 by inhibiting the nonselective combustion
of reductant under the action of catalyst. The absolute amount of unburned HC in the
exhaust is low, and diesel engines need adding a little more reductant to purify NOx since
they adopt oxygen-enriched combustion technology. According to the differences of
additional reductant, SCR can be divided into urea selective reduction of NOx (Urea-SCR)
and HC selective reduction of NOx (HC-SCR). HC-SCR technology uses hydrocarbon
fuel as reductant and zeolite or Ag substrate (Ag/Al2O3) as a catalyst generally, so the cost
is relatively low. Its advantage is that the catalyst has high initial activity, and the
disadvantages are that hydrothermal stability is poor, sulfur resistance is low, low-
temperature activity is not ideal, and practical application is limited.
Urea-SCR technology is developed based on the ammonia selective reduction of NOx
(NH3-SCR) technology. But as one kind of gas, ammonia is too difficult to move and
store. Ammonia is also highly corrosive, prone to leakage, while urea is characterized by
non-toxic, clean, odorless, non-flammable, no explosion danger and low corrosive. So we

ISSN: 1975-0080 IJMUE

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use an aqueous solution of urea instead of ammonia generally in the current, and use the
ammonia from urea thermal decomposition to restore the NOx of diesel exhaust. Urea -
SCR has been used all over the world widely as the most mature post-processing
technology of NOx.

2. Structure of System and Chemical Reaction of SCR

A typical Urea-SCR system includes urea storage device, urea supply system, catalytic
converters and control unit, as shown in Figure 1.

Figure 1. Schematic Diagram of Typical Urea-SCR System Structure

When SCR is working, the control unit performs the predefined control strategy. Then
the urea solution in the storage device is sucked by the supply pump and injected into the
exhaust pipe in front of the catalysts through the nozzle of urea supply system. The urea
reduces into reductant NH3 by heating, as shown in formula (1). On the surface of the
SCR catalyst, the NOX is reduced to N2 by NH3, its main formula of reaction as shown
in (2) and (3):

(NH3)2CO2+H2O→2NH3+CO2 (1)
4NH3+4NO+O2→4N2+CO2 (2)
4NH3+2NO+2NO2→4N2+6H2O (3)

In high-temperature environment (higher than 300 ℃), NOx in the exhaust gas can
quickly react with ammonia (NH3) to form N2 and H2O under the action of the catalyst.
The temperature of diesel engine exhaust is generally in the range of 300 ~ 500 ℃, it
meets the temperature conditions that NOX reduction needs.

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3. Present Status of Urea-SCR Technology

The most ideal working conditions of Urea-SCR system is to ensure a low escape rate
of reductant NH3 on the premise of achieving a high conversion of NOx. To meet these
two requirements, we must ensure the following three performance indicators: good level
of droplet evaporation and pyrolysis, reasonable space velocity distribution, reasonable
concentration distribution of the reductant. SCR supply system should ensure that the
liquid droplet can be reacted completely for evaporation and pyrolysis before entering the
inside of the catalytic converter carrier. And reasonable space velocity distribution is to
ensure that reductant and reactant have plenty of contact and reaction time. Moreover
reasonable distribution of reductant is the determinant conditions that avoid excess
ammonia coefficient too high or too low. The current studies are going largely around the
urea storage device, urea supply system, catalytic converters, control unit and three
performance indicators that are mentioned later in this article.

3.1 Urea Storage Device

Urea storage device, which is used for storing the urea solution, mounts transducer,
heating device and ventilation device at the top and the screw holes to release the residual
liquid at the bottom. Transducer includes temperature sensor and level sensor, which can
sense the temperature and height of the urea level.
It consists of two parts to research urea storage device: the stability of solution and the
adaptability to the environment. Urea solution is alkaline, the PH of which is 8.8. And its
corrosion for copper, cast iron, solder and aluminum is serious. So we must use special
materials such as austenitic steel to make its storage, pipeline transportation and filling.
The urea storage device generally uses urea aqueous solution which concentration is 32.5
％, the most important reason is the lowest freezing point of the solution (-11℃). Even if
the concentration of the urea aqueous solution is in a semi-frozen state, the solution
concentration remains unchanged. Not only that, the concentration of solution can still
keep unchanged for a long time in normal storage conditions. So it is suitable for long-
term preservation in process of transport or storage. And it also meets the requirement that
vehicle is not used for a long time.
When the temperature was lower than the -11℃, urea solution began to crystallize. The
storage container, pipeline, pump and nozzle need to be heated in the environment
temperature less than -11℃ to prevent crystallization. Urea tank, which has the low
temperature heating device, uses engine circulating water heating in general.
In addition, there are a lot of alternatives of urea solution, including the solid urea,
ammonium salts (such as ammonium carbamate), chloride salts (such as magnesium
chloride) storage technologies of ammonia [1-2]. Part of the solution can make the
freezing point of urea solution to - 30 ℃.
FEV company in 2009 showed solid selective catalytic reduction (SSCR) system on the
Dodge Ram Pickup Truck [3], which declared the SSCR technology has entered a
practical stage. Ammonia’s solid precursor using ammonium carbamate. In the container,
ammonium carbamate decomposition heated cyclically by oil produces ammonia.
Working state of heating device was adjusted by control system according to pressure and
temperature in the container. Generated ammonia was sprayed into exhaust pipe through
quantitative injection device.
Patent of Germany’s MAN commercial vehicle company in China [4], provides a
means and device for solid urea pellets with grinding and pyrolysising to produce
ammonia. U. S. patent of Theodore J, et al. [5], provides an apparatus and method for
production of ammonia by solid urea pellets.
However, it still need further study about additional heat source, influence of fuel
economy, the response characteristics of the release of NH3 and other issues.

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3.2. Urea Supply System

The main function of the urea supply system is that urea is dispensed from the storage
device in accordance with the requirements of the controller and transported to the nozzle
with a certain pressure. But the urea will be withdrew in the line to urea tank when the
system to be turned off. Urea supply system consists of the following parts: the urea
supply unit, the air assist unit, measuring injection system, connecting pipes, all kinds
of sensors and heating devices etc.
There are two main types of urea supply unit: one is represented by Grundfos
company, another is represented by Bosch company. The first unit uses a stepper motor to
drive a constant volume of plunger reciprocating motion and achieves the control of
supply by controlling the speed of the motor. The second unit achieves the control of
supply by controlling the solenoid valve, which is controlled by a PWM. But it must
adopt a urea pump to build a constant pressure in the line before the solenoid valve.
Urea supply system is divided into two types: air-assisted and non-air-assisted. Urea
supply system that used the compressed air-assisted was relatively common at the
beginning of researching the automotive SCR technology, such as Bosch, Grundfos and
Albonair. Then the urea supply system which had non-air-assisted appeared gradually,
and it was putted into business operations successfully. Air-assisted system uses
compressed air, and it uses metering pump for controlling the injection amount of the urea
solution commonly. Experiment and simulation results show that the effect of air-assisted
spray atomization is good [6]. And air-assisted promotes the decomposition of urea. It can
save the cost at the same time because the original car brings air compressors. Non-air-
assisted supply system establishes pressure through the urea pump. Urea solution does not
need compressed air because it can achieve spray under the high pressure. In addition, the
advantages of non-air-assisted include simple system principle, fewer parts, tight
structure, low failure rate and precise control. Their disadvantages are that the effect of
spray is poor. And nozzle needs to be cooled down because of its complex structure.
Figure 2 shows a set of non-air-assisted urea supply system. Under the action of the
motor in the urea pump, urea solution in the urea tank is sucked up, and reaches the urea
injection unit after the urea pump, and the end injects into the exhaust channel through the
nozzle. Dosing Control Unit (DCU) is used to control the injection quantity and injection
timing of urea solution. First the rotation of the urea pump motor is controlled by DCU,
so that the pipeline pressure before urea injection unit is stable in the numerical value of
calibration. Excessive urea solution goes back to the urea tank through backflow inlet.
Then according to the current state of exhaust to determine the required amount of urea,
by adjusting the pulse width of PWM signal to control the opening time of urea injection
unit, the corresponding amount of urea solution sprayed into the exhaust channel, in order
to achieve the measurement and atomization of urea. The cooling of urea injection unit is
accomplished by the engine cooling liquid, and the working temperature is not more than
140℃.

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Figure 2. Non-Air-Assisted Urea Supply System

Figure 3 shows a set of air-assisted urea supply system. The metering of urea solution
is accomplished by the diaphragm pump. Stepping motor through the belt drive eccentric
wheel, then the eccentric wheel drive the plunger reciprocating movement, and the
diaphragm is finished under the action of the plunger to the suction and extrusion process
of urea solution. Diaphragm working chamber volume is fixed, so the stepper motor each
push a diaphragm, quantitative 0.8ml urea solution is supplied. According to the
measurement and control unit of instruction, in different speed of motor work, the
corresponding demand for urea is provided. The urea solution from diaphragm reaches the
mixing chamber through a one-way valve, and is mixed with the high pressure air
supplied by the air compressor. The final urea solution in the compressed air blowing
reaches atomizer to achieve atomization. A sensor for monitoring the pressure of the
pipeline is arranged on the urea pipeline in the mixing chamber. Under normal operating
conditions, the pressure of compressed air so that the air valve urea return port blocked. If
the pressure sensors to monitor the urea solution pressure is too high, the control unit send
instructions to air solenoid valve to reduce the air pressure before executing valve, thereby
opening a reflux inlet, excessive urea goes back to the urea box by reflux inlet.

Figure 3. Air-Assisted Urea Supply System

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Injection system of measurement is an important research domain in Urea – SCR. Its

function is that urea solution can be sprayed into the exhaust pipe by fog according to the
demand of Urea under the control of the Data Controlled Unit (DCU). Generally this
system improves the quality of urea injection through improving nozzle structure and
strengthening its atomization characteristics. It also improves the atomization results by
improving the pipeline shape, position and angle of the spray. This way can promote the
decomposition of urea, and it also can reduce the formation of deposits [7].
There are two methods to the mature technology of decomposing urea into NH3:
pyrolysis and hydrolysis. Currently the SCR of vehicles takes pyrolysis technology. This
technology supposes that urea pyrolysis and catalytic going at once in an ideal world. The
urea solution can be decomposed completely before entering the catalyst, and NH3 mixes
with the engine exhaust. But in actual condition, the distance between the urea aqueous
solution injection and the catalyst entrance is very short, the decomposition of urea at the
entrance is not sufficient. It also cannot guarantee that reductant and exhaust could be
mixed uniformity, and it generates other by-products. The test indicates that, a mixture of
NH3, HNCO and urea enters into the catalyst due to the more undecomposed urea at the
entrance of catalyst. HNCO has a polymerization with urea to biuret easily at higher
temperature (about 150~200℃) because its activity is very high. It may form cyanuric acid
and react with NH3 to ammelide, ammeline, melamine and so on [8-10].
The rate constants of the quasi first order reaction of HNCO can be calculated by the
following formula:

V 3
k  In (1   )[ cm /( g.s )]
W (4)

In the formula, k is rate constant; V is gas flow velocity under the actual temperature
and pressure; W is the quality of catalyst. Figure 4 is the relationship between the reaction
rate constant and temperature of HNCO in 4 different catalysts. From the diagram, at low
temperatures, the reaction rate constants of HNCO under different catalysts are different,
but the gap is gradually decreased with the increase of temperature.

Figure 4. Reaction Rate Constants for Hydrolysis of HNCO for Catalysts

As shown in Figure 5, urea sediment can be divided into urea crystallization and urea
stone according to the process of formation. Urea crystallization is due to the loss of water
in urea solution which leads to over saturation and production of urea, which is the

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product of process of physical reaction. With the increase of temperature, urea

crystallization can continue to be decomposed. Urea stones were caused by the by-product
caused by side effects of urea decomposition process, which belongs to chemical reaction
products. Urea stones need a higher temperature to decompose. Because the quality of
urea droplets is much larger than that of gas, the remain in the airflow stagnation zone can
be formed crystallization, and if it cannot be decomposed completely in time, it will be
the core of continuous growth. Because the crystallization cannot be completely
decomposed, and ultimately urea stones were formed. Urea stones is accumulated to a
certain extent, it is possible to plug the urea flow channel, and therefore the analysis of
sediment generation need to study the process of urea decomposition carefully.

Figure 5. Urea Sediment and its Analysis

The Ford Motor Co studied the urea by experiment, the results showed that the
sediment was produced by a period of time after a period of time under 300℃, and the
main component of sediment was cyanuric acid and urea. But the sediment was not
formed at 350℃ [11].
Navistar company of the United States also carried out the study, the results show that
in the low exhaust temperature, low ambient temperature, relatively large urea solution
injection volume and relatively small exhaust flow, the sediment is the most easy to
produce. Under these conditions, 25-65% injected urea solution is converted to the
sediment. When the temperature is raised to 350℃, the amount of the injected urea
solution converted is less than 1% [12].
Weichai Power Technology Center Yu Jiao’s research [13] shows that in SCR system,
urea decomposition deposition is an important factor that affects the efficiency of the
catalytic converter. And urea decomposition and injection quantity and exhaust
temperature have great relationship. The spray nozzle position of urea deposition is due to
the nozzle flange design is not reasonable. In the position urea deposition was produced
by the presence of a exhaust flow vortex. Urea deposition in the exhaust pipe is that urea
injection angle is not reasonable. Urea solution is injected into the wall, and the wall
temperature is reduced, so the result is deposition of urea in the wall. Urea deposition in
SCR catalyst inlet is caused by no completely evaporation of the injected particles or the
excessive amount of injection.
Some researchers [14] have studied and achieved some results by optimizing the
arrangement of SCR system to improve the conversion efficiency of NOx at low
temperature and reduce the sediment generation, but it also needs further research to be
able to effectively prevent the generation of sediment.
These deposits may clog the nozzle of urea and the catalyst carrier. It also may affect
the activity of catalyst and increase the consumption of urea. These repercussions bring
about the difficulty to control the SCR system. Thus the cryogenic sediment of urea is a
hot issue of SCR field in the current [15-16].

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It is common practice to install mixer before the SCR catalyst for promoting the
evaporation, decomposition of the urea and the mixture of exhaust. Numerical simulation
and experiment show that mixer is helpful to reducing the generation of sediment and
improving conversion efficiency of SCR [17-19].

3.3. Catalysts
Catalyst has three basic parts: the coating, carrier and package [20]. The study of
catalyst focuses on the choice of chemical reaction coating, internal carriers of catalyst
and the design of muffler.
Coating what consists of water coating and activity components of catalytic is the core
of the catalyst [21]. Urea-SCR catalyst bases on vanadium-based catalyst (TOi2-V2O5)
and zeolite catalyst. The advantages of vanadium-based catalyst are high conversion
efficiency, high and wide temperature window, good resistance to sulfur and low cost.
But the volatilization of vanadium will lead to inactivate when the temperature is higher
than 600 ~ 800 ℃. The temperature from heavy engine to the surface of catalyst cannot
reach such a high level, so it is applied to the domestic heavy engine. By comparing
conversion efficiency of NOX with Fe, Cu zeolite catalyst and alumina-based catalyst, we
can know that Cu zeolite catalyst have a good low temperature performance. Fe zeolite
catalyst have a good high temperature performance, while the performance of alumina-
based catalysts is somewhere in between. However, the composite zeolite catalyst of
copper and iron can integrate the all advantages [22-24].
The conventional coating application of SCR catalyst also includes catalyst that is used
to remove ammonia. This catalyst is named AMOX (Amm on Oxidation catalyst). And it
is also be used to remove NH3 that is remained after the main reaction of SCR.
Alternative technology is that we installs the after-oxidation catalytic converter after the
SCR catalyst. But there are problems with these solutions. Not only may oxidise these
solutions from NH3 into NOX as to increase pollution and system cost, but also cause
waste of urea injection to a certain degree. So we place the before-oxidation catalysts
before the SCR catalyst as the pretreatment device of engine exhaust generally.
Carrier is the skeleton part of SCR system, AMOX and coating are coated on the
carrier. Most of carrier is a whole which has cylindrical cellular channel. Its basic material
can be divided into two categories: metal and ceramic based. Metal-based carrier is small,
and it can be made into various shapes to make the design of catalytic converters easy.
But the cost of it is higher. Ceramic carrier is mainly composes of silicon carbide and
cordierite. Cordierite is mainly used in heavy engine. The advantages of cordierite are
high temperature resistance and high mechanical strength. Its disadvantages are the poor
corrosion resistance and small thermal conductivity. In addition, there is a poisoning
effect on the noble metal catalyst because cordierite contains a large of SiO2 (55% or
more). SiC mainly is applied to small-displacement engines. It has better performance
than cordierite [19]. The advantages of SiC are high porosity and strong thermal diffusion
ability. The disadvantages are high cost of preparation and the need of adhesive for a
bigger volume. Its wall thickness and porosity of the carrier are affected by the accuracy
of machining, durability of catalysts and influence of packaging process.
Package for SCR catalyst that is used to connect the carrier with the exhaust pipe is the
outer packing of carrier. It can be divided into packages with silencer and without silencer
according to the different functions as the outer packing of carrier. It also can be divided
into boxes and barrels type package depending on the arrangement of whole vehicle. Box
package’s advantages are remarkable noise-reducing effectiveness, lower airspeed and
higher efficiency of catalytic reaction. But there is a certain degree of difficulty on vehicle
layout because of the large volume. It is suitable for large vehicles and trucks. Barrel type
package is convenient for layout because the volume of post-processor close to the
muffler of original vehicle. Its performance is slightly worse than the box-type post-
processor due to the lack of structural design of muffler and the high airspeed of catalytic.

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So the barrel type package is mainly suitable for small space vehicles and city buses. The
most important parameters of diesel SCR catalytic converter package are the uniformity
of flow field and entire backpressure of catalytic converters.

3.4. Control Unit

The control unit of Urea-SCR collects signals from the operation condition of the
engine ECU and the sensor of SCR system. It also treats with these signals. And it can
calculate the demand for urea according to the strategy of urea injection. At the same
time, it takes the signal to the corresponding execution unit and controls the urea
injection. In addition, it has the function of fault inspection and diagnosis. Progress in the
control unit is mainly reflected in two aspects: software and hardware. The key of
hardware is the further study of the sensor, and the key of software is the control strategy
of urea injection.
The control strategy of urea injection can be divided into open-loop control and closed-
loop control from the structure. The main difference is whether it uses signal of NH3
sensor (or NOx sensor) which is loaded in downstream of SCR for feedback control. SCR
open-loop control strategy system doesn’t have the ability to correct automatically or
compensate. SCR closed-loop control strategy can improve the accuracy of the control
and stability, and the response time is shortened. However, there is still a lack of sensor
sensitivity and the cost issues, owing to the cross-sensitivity of NOx sensor and the
immature technology of NH3 sensor [25-27]. Current solutions include stimulus-response
method and adding post-oxidation catalytic converter.
The urea injection control strategies of SCR system can be divided into mapping based
on pulse spectrum [28] and model based on calculations from the controller design [29].
The control strategy of model based on calculations is complexity, and it has few
applications. The structure design ideas of open-loop urea injection control strategies
based on the pulse spectrum is simple, and its development difficulty is low. So there is
more widely application in engineering.
SCR system requires fine control of urea to meet the strict emissions standards.
However, feedback control and the optimization of control strategy are very difficult
because the SCR system involves many aspects.

4. Conclusions
Follow the author information by two blank lines before main text. For the present,
with the increasingly strict emission standards, the optimization of fuel economy and
system design costs will become an important constraint condition to the control of diesel
engine emission. In this condition, the main research of urea storage device focuses on
alternatives of urea and storage problem of urea solution under the low temperature. The
research direction of urea supply system is that we need improve the low temperature
properties of SCR technology and the efficiency of the decomposition of urea. Catalyst is
the core of SCR technology research, and it trends for reducing the installation dimension
and cost of the system under the premise of meeting emission standards. In addition, it
will develop a new type of catalyst and reductant. The main research direction of control
unit is that we need develop new sensors and more precise control strategies.
In recent years, China increases investment in science and technology for
environmental protection. It makes great progress in the overall level of science and
technology, and it reaches or approaches international advanced level in some areas.
Research Center for Eco-Environmental Sciences, Tsinghua University, the PLA
Academy of Military Transportation, China Environmental Science Research Institute and
many other domestic research institutes all study for purification technology of diesel
exhaust. Dalian University is studying the closed-loop control strategy of SCR based on
pulse spectrum. Experiments show that this strategy can improve the catalytic efficiency

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of SCR, and it also can reduce the difficulty of the SCR system control. So it will achieve
more precise feed control. This SCR can open a new direction of diesel engine exhaust
gas purification.

Acknowledgements
This paper is supported by the National Natural Science Foundation of China
(51306025) and the Fundamental Research Funds for the Central Universities
(2572015AB13), and Project supported by the Maor International Joint Research Program
of China (Grant No. 2013DFA71120).

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