Applied Thermal Engineering 128 (2018) 1382–1390

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Applied Thermal Engineering

journal homepage: www.elsevier.com/locate/apthermeng

Research Paper

Analysis of composite sorbents for ammonia storage to eliminate NOx

emission at low temperatures
Z.X. Wang, L.W. Wang ⇑, P. Gao, Y. Yu, R.Z. Wang
Institute of Refrigeration and Cryogenics, Shanghai Jiao Tong University, Shanghai 200240, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

A novel system of composite sorbent- A composite sorbent-SCR system for ammonia storage/release to eliminate NOx emission at low temper-
SCR is proposed and analyzed. atures is proposed for diesel vehicles.

The NH3 storage capacity of
composite sorbent is studied.

The weight of composite CaCl2 is
250% lighter than AdBlue for same
mileage.

The de-NOx efficiency of composite
sorbent-SCR is the better at low
temperatures.

The cost of NH3 supply part of
composite sorbent-SCR is 76%
cheaper than urea-SCR.

a r t i c l e i n f o a b s t r a c t

Article history: A new type of composite sorbent-SCR system has been designed for NOx elimination of diesel vehicles to
Received 21 July 2017 promote the NOx conversion rate at low temperatures (50–250°C), with the sorption reaction tempera-
Revised 15 September 2017 ture of 50–100°C for safety reason. NH3 is sorbed by composite sorbents with expanded natural graphite
Accepted 17 September 2017
treated with sulfuric acid (ENG-TSA) matrix at room temperature, and released from composite sorbents
Available online 19 September 2017
by heating phase, which is driven by both electricity and exhaust waste heat. The composite sorbent is a
porous composite of 80% chemical sorbents and 20% ENG-TSA. The NH3 sorption capacity of chemical sor-
Keywords:
bents (NH4Cl, NaBr, BaCl2, CaCl2 and SrCl2) have been evaluated and compared with traditional urea-SCR
Composite sorbent-SCR
NOx elimination
system with AdBlue, and the results are analyzed. NH3 cannot be pyrolyzed from AdBlue below 160°C,
NH3 sorption capacity and the NOx conversion rate of the composite sorbent-SCR system is about 45% higher than the urea-
Low cost SCR system (0%) at 50°C. NH4Cl and NaBr are not suitable for composite sorbent-SCR system for that
the pressure is too high even at the environmental temperature. According to the NH3 sorption capacity,
composite of CaCl2 with ENG-TSA and composite of SrCl2 with ENG-TSA are both optimal solid sorbents,
and between them CaCl2 with ENG-TSA as matrix is the best choice for the small mass required and the
low cost.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction exhaust of HC, CO and soluble organics (SOF); DPF technology is

Diesel exhaust purification technology includes diesel oxidation
catalyst (DOC), diesel particulate filters (DPF) and de-NOx cleaning
catalyst (De-NOx). DOC technology is mainly used for processing
⇑ Corresponding author.
E-mail address: lwwang@sjtu.edu.cn (L.W. Wang).
used to deal with the small particles of exhaust; De-NOx technol-
ogy, as the name implies, is used to eliminate nitrogen oxides.
The De-NOx technology has attracted more attention for that the
NOx emission of diesel vehicles, NOx has serious negative impact
on the health of people. In European the emission standard for
NOx emission of diesel vehicles were increasingly strict from the
Euro Ⅰ (8.0 g/km) in 1992 to the Euro VI (0.5 g/km) in 2012. As

https://doi.org/10.1016/j.applthermaleng.2017.09.084
1359-4311/Ó 2017 Elsevier Ltd. All rights reserved.
 Z.X. Wang et al. / Applied Thermal Engineering 128 (2018) 1382–1390
Nomenclature
A sectional area (m2)
ASS ammonia sorption storage
c specific volume (kJ/(kg °C))
CCS composite chemisorption sorbents
DOC diesel oxidation catalyst
DPF diesel particulate filters
ENG expanded natural graphite
ENG-TSA expanded natural graphite treated with sulfuric acid
GHSV gas hourly space velocity
g gracity acceleration (9.80 m/s2)
HC-SCR hydrocarbon selective catalytic reduction of NOx
HTSs high temperature salts
K coefficient
LTSs low temperature salts
m mass (kg)
MTS-NH3 MTS that has adsorbed ammonia for saturated state
MTSs middle temperature salts
n coefficient
NH3-SCR selective catalytic reduction by using ammonia source
NSR storage-reduction technology
p pressure (Pa)
PM particulate matter
Q heating (kJ)
SCR-CC SCR catalytic converter
the country strictest for diesel vehicle emission, the United States
had implemented the emission limit of 0.8 g/km NOx in 2007,
which was much lower than the Euro Ⅴ standard (2.0 g/km) in
2008 [1–7]. It is obvious that people want to achieve zero release
of NOx pollutant, although the Volkswagen’s emission cheating
event revealed that it is a formidable task to realize.
Referring to NOx purification technology of diesel engine, the
existing and proven technical proposal are mainly ammonia selec-
tive catalytic reduction of NOx (NH3-SCR), the hydrocarbon selec-
tive catalytic reduction of NOx (HC-SCR), storage-reduction
technology (NSR), NOx and PM purification technology and
four-way catalytic technology [8]. At present, the most popular
de-NOx technology which has been widely applied in the world-
wide top automobile factories is urea-SCR technology, namely a
kind of NH3-SCR technology.
For the liquid material as ammonia source, urea solution is
selected to reduce NOx for many years, instead of ammonia-
water solution. Urea solution can be decomposed into NH3 in
exhaust pipe with the heating effect of exhaust gas, and then reacts
with NOx completely in catalytic converter and converts it to N2
and H2O. According to the latest data provided by Bosch Company,
the maximum volume flow of 50 ml/min is required for the 80%
NOx conversion. Hu [9] obtained a diagram of NOx conversion effi-
ciency vs. fuel injection quantity by multiple experiments, and in
the downstream of catalyst the maximum NH3-leakage hypothet-
ical limitation is 10 ppm. According to Hu’s data, the NOx conver-
sion efficiency is greater than 80% all the time when the fuel
injection is 75–225 mg/hub and engine speed is 1000–1900 rpm.
However, urea-SCR technology has many problems during prac-
tical application, such as the high cost, low NOx conversion effi-
ciency at low temperatures, urea crystallization, coking under the
condition of incomplete decomposition, and low effective ammo-
nia content (theoretical ammonia content is around 18.42% for
32.5% urea solution). Hence, developing a new technology with
better performance for ammonia storage is important for the
development of de-NOx technology.
1383
SCR-ECU SCR electronic control unit
SEM scanning electron microscope
T temperature (K, °C)
v specific volume (m3/kg)
V bulk volume (L)
x adsorption quantity (kg/kg)
Subscripts
0 maximum value for saturated state
a Point 2 in Fig. 2
ad adsorbent or adsorption process
ad,max maximum value of adsorption
ad,min minimum value of adsorption
c cooling
ch chemisorption
des desorption process
e Point 1 in Fig. 2
g Point 3 in Fig. 2
h heat
i condensation
s saturation
A_B AdBlue
D_O diesel oil for 100 km mileage
NH3 adsorbed ammonia
Some researchers have made efforts on finding new type of
NH3-SCR technology. Cottle John [13] first proposed an idea of stor-
ing ammonia with the help of dissolved salts in 1959, and designed
a storage-obtain ammonia recovery system. In 1992, Walker and
Speronello [10] summarized the design and development of
ammonia injection system, and proposed that Teflon and stainless
steel can be used as the raw material of ammonia injection equip-
ment. His-Jen Chen and Mann-Hsing Lin [14] designed a computa-
tion model to determine the thermal response of ammonia unit
when it was put on fire in 1998. It is good to avoid the safety prob-
lems of ammonia storage. From the beginning of the 21st century,
the solid sorption ammonia storage technology has been gradually
paid more attention. In 2007, Kaboord et al. [15] designed a cylin-
drical honeycomb-like sorption bed using molecular sieve as
adsorbent, and proposed a complex sorption based ammonia stor-
age and regeneration system accompanied with two ammonia con-
tainers. Chun and Ken-ichi in 2004 [16] and Elmøe et al. in 2006
[17] studied on CaCl2-CaBr2 mixture and MgCl2 sorbent for ammo-
nia storage technology. Later in 2008, Johannessen et al. [11] found
that the storage volume of Mg-based complex and Ca-based com-
plex to release ammonia is approximately triple to urea’s. Janna V.
Veselovskaya and Mikhail M. Tokarev [29] proposed a novel com-
posite sorbent of ammonia BaCl2/vermiculite and studied the
dynamics of quasi-isobaric ammonia sorption/desorption on the
novel composite sorbent in 2011. And Gary Fulks et al. [12] carried
out a series of experiments in 2009 to investigate the performances
of different ammonia sources, including 3 types of urea, 9 types of
ammonia salt, 9 types of metal ammines and 2 types of baselines
(anhydrous liquid ammonia and acetone), and they found that
ammonium salts and metal ammine chlorides had the best
performances.
Developing solid material as ammonia source is a safer and
more stable method. For chemical solid sorbents, metal halides
always have attenuation. In order to solving this problem, the com-
posite sorbents had been studied, and results show that both heat
and mass transfer performance were improved significantly. Wang
1384 Z.X. Wang et al. / Applied Thermal Engineering 128 (2018) 1382–1390
et al. [18] studied the composite sorbents for enhancing heat and
mass transfer performance and increasing the sorption quantity
simultaneously, and also summarized the methods of developing
composite sorbents in details. Refs. [19–21] tested and studied
the composite sorbents with expanded natural graphite (ENG)
and expanded natural graphite treated with sulfuric acid (ENG-
TSA) as matrix, and the results of ENG-TSA matrix showed much
higher thermal conductivity and reasonable permeability. The
experiments and researches in references [22–23] made significant
efforts on improving the sorption quantity and sorption rate. But
the application of composite chemisorption sorbents (CCS) was
mostly analyzed for refrigeration and energy storage, and hasn’t
been studied for dealing the NOx emission.
In this paper, a type of composite sorbent-SCR is proposed, and
the gas of NH3 is released from the solid ammonia source and jet-
ted to the exhaust pipe directly. Different composite chemical sor-
bent (with ENG-TSA as matrix)-NH3 working pairs are analyzed
and compared for dealing the NOx emission.
2. Working principle
The ASS unit is installed in the position where AdBlue box and
AdBlue pump were mounted under the truck underframe. And the
ASS unit is nearby the exhaust pipe, which can make the utilization
of exhaust heat more convenient and make the connection of the
whole composite sorbent-SCR system easier.
2.1. Two working phases in one cycle
For the NOx converting process, the composite sorbent-SCR
system (Fig. 1a) consists of an ASS unit, a SCR catalytic converter
(SCR-CC), a SCR electronic control unit (SCR-ECU), a nozzle, valves,
several sensors, several connecting lines and some pipelines, etc.
More details, the SCR catalytic converter mainly includes carrier
(usually shaped as honeycomb structure), catalyst and encapsula-
Fig. 1. Working principle of the system. (a) Desorption and de-NOx phase; (b) NH3
sorption and storage phase.
Fig. 2. Clapeyron diagram of chemisorption.
tion. The sensors mainly include the temperature sensor, the pres-
sure sensor, the NOx sensor and the NH3 sensor. A pipeline branch
is designed for safety consideration, and two electromagnetic
valves are used to control the exhaust flow (indirectly control the
reaction temperature). Two working phases, i.e. NOx converting
and NH3 sorption processes, are involved in one cycle of the com-
posite sorbent-SCR system.
(1) Desorption and de-NOx phase (Fig. 1a). The ASS unit is driven
by both electric heating and exhaust gas. Before the vehicles
are started, the system is pre-heated by the electricity for
prompt inject. After the vehicles started, the heating source
will be switched to the exhaust gas for saving the energy. In
the initial heating phase both the temperature and the pres-
sure in the ASS unit increase. The ammonia is desorbed
when the pressure in the unit is higher than equilibrium
reaction pressure. After that the NH3 gas is ejected by nozzle
and flows to the exhaust gas pipe and mixes with the NOx in
the exhaust gas. The mixture reacts thoroughly in SCR-CC,
and the reaction products go through the NOx sensor, which
returns the feedback signal to the SCR-ECU. After that the
SCR-ECU adjusts the NH3 injection quantity according to
the NOx content in final exhaust. The reactions of eliminat-
ing gaseous pollutant of NOx as well as CO, CO2, and other
particulate matter (PM) pollutants are catalyzed in the
SCR-CC.
(2) Sorption and storage phase (Fig. 1b). After all the stored
ammonia in ASS unit is used up, the NH3 sorption and stor-
age process is required. In this process, the ASS unit is con-
nected with the ammonia tank. The ASS unit can be cooled
by external cooling method, and both temperature and pres-
sure decrease. The ammonia tank is heated by the environ-
mental medium, and its temperature is kept at least 5°C
higher than the sorption temperature inside the ASS unit
to avoid the condensation to happen inside the unit. When
the pressure inside the ASS unit is lower than the pressure
of ammonia tank, the valve is open, and the ammonia is
sorbed in the ASS unit until it reaches saturation.
2.2. Clapeyron diagram for chemisorption cycles
The chemisorption has both features of absorption and adsorp-
tion. One hand the reaction occurs both at the surface and inside
the sorbents which is the absorption feature, on the other hand
the solid-gas reaction is the adsorption feature. So it is generally
classified as the solid sorption or chemisorption other than adsorp-
tion or absorption. The Clapeyron diagram of chemisorption work-
ing pairs is shown in Fig. 2. Theoretically the chemisorption
working pairs generally has one variable, i.e. p or T. Corresponding
 Z.X. Wang et al. / Applied Thermal Engineering 128 (2018) 1382–1390
to two working processes shown in Fig. 1, the NOx reaction process
is 2–3 and point 3, and the NH3 sorption process is 3–2, point 2 and
point 1. For NOx reaction process firstly the solid sorbent is heated
along 2–3 with sensible heat of Qin to point 3, and then the desorp-
tion happens at point 3 driven by the heat quantity of Qdes. The
released NH3 is injected into the exhaust pipe reacting with NOx
pollutant by ejector. For the ammonia sorption and storage pro-
cess, the sorbent bed is cooled from point 3 to point 2 with releas-
ing the sensible heat of Qin, and the sorption happens at point 2, for
which the 1–2 is the chemisorption process along with the release
of chemisorption heat Qch.
The heat and mass transfer performance is the key factor for the
ASS unit because the fast sorption storage and prompt ammonia
releasing processes are required. Research shows that the additive
of ENG-TSA can improve the heat transfer performance signifi-
cantly without the influence on mass transfer [25]. The composite
sorbent is also the solution for the performance attenuation of the
long term usage [27]. Thus the composite sorbents are developed.
3. Theoretical performance analysis of metal halides-NH3
chemisorption
Equations of sorption quantity and cycle sorption quantity are
proposed. Chemical reaction processes of metal halides are also
concluded in this part. The weight of ammonia source of chemical
sorbent-NH3 for 100 km is calculated and listed.
The cycle sorption quantity is the difference of maximum and
minimum sorption quantity for points 2 and 3, respectively:
Dx ¼ xad; max  xad; min
For the injection process of NH3 the pressure of ASS unit is gen-
erally 2 bar larger than the pressure at the outlet of nozzle, which
is 2 bar. That means the pressure inside the ASS unit should be
around 4–5 bar. For the heat exchanging process between the
exhaust gas and ASS unit, the temperature of the unit is generally
lower than 250°C for that the heat transfer coefficient of the gas is
quite low. Considering the safety problem, the desorption temper-
atures is controlled at 50°C to 100°C by the pipeline branch design.
And considering that better sorption performance and faster sorp-
tion rate can be gotten under the condition of lower cooling tem-
perature, the sorption temperature should be adjusted as the
season changes for getting best cooling effect.
Two typical diesel vehicles are analyzed. One is the small type
vehicle (type-A) with engine displacement of 2 L which is about
7 L fuel consumption per 100 km, another is the large type vehicle
(type-B) with engine displacement of 7 L which is about 35 L fuel
consumption per 100 km. For type-A truck the required NH3 is
30–50 g per 100 km, which is calculated by the relation of NOx
emission and the diesel consumption [35]. In the same way, for
type-B truck the required NH3 is 150–250 g per 100 km. The sorp-
tion needed for storage the NH3 is calculated by the cycle sorption
quantity, and the equation is:
mam
mad ¼
ðxad  xdes Þ
The sorption quantity of different metal halides is different. The
ideal condition is the equilibrium condition for that the sorption
hysteresis does not exist, and the chemisorption process and des-
orption process are completely reversible. For different halides
the ideal condition is the equilibrium condition for that the sorp-
tion hysteresis does not exist, i.e. the chemisorption process and
desorption process are completely reversible. The heat transfer
coefficient of the exhaust gas is very low, thus the heat transfer
performance between the exhaust gas and ASS unit is critical.
The temperature of ASS unit commonly is lower than 200°C. High
1385
temperature salts (HTSs) need high heat source temperature for
desorption, which is generally higher than 200°C [31]. Simultane-
ously, it also requires high desorption heat that accounts for the
high desortion enthalpy. Thus, it is not the optimal choice. In the
study, low temperature salts (LTSs) such as NH4Cl, NaBr and BaCl2
and middle temperature salts (MTSs) such as CaCl2 and SrCl2 are
selected. The equations for LTS are as follows [32]:
NH4 Cl  3NH3 þ DH1 $ NH4 Cl þ 3NH3 ð3Þ
NaBr  5:25NH3 þ DH3 $ NaBr þ 5:25NH3 ð4Þ
BaCl2  8NH3 þ DH2 $ BaCl2 þ 8NH3 ð5Þ
The reaction of LTS-NH3 complex is one step, whereas the reac-
tion of MTS-NH3 complex is multi-step. The equations of MTS are
as follows [30–31]:
CaCl2  8NH3 þ DH4 $ CaCl2  4NH3 þ 4NH3 ð6Þ
CaCl2  4NH3 þ DH5 $ CaCl2  2NH3 þ 2NH3 ð7Þ
CaCl2  2NH3 þ DH6 $ CaCl2 þ 2NH3 ð8Þ
SrCl2  8NH3 þ DH7 $ SrCl2  NH3 þ 7NH3 ð9Þ
SrCl2  NH3 þ DH8 $ SrCl2 þ NH3 ð10Þ
High temperature (about 250°C) is needed for Eqs. (8) and (10)
under the condition of 4 bar saturated pressure [31], hence when
the exhaust temperature is below 300°C (considering the heat
ð1Þ transfer temperature difference) the reaction shown in Eqs. (8)
and (10) won’t occur.
The Clapeyron equilibrium curves of different metal halides-
ammonia working pairs are shown in Fig. 3.
The ammonia storage amount of single metal halides and the
weight of sorbents are concluded in Table 1. The desorption pres-
sure is supposed to be 4 bar, and the corresponding desorption
temperature is also show in Table 1. The chemisorption tempera-
ture is determined by the environmental temperature, i.e. the
ASS unit exchanges the heat with the heat sink at the environmen-
tal temperature. According to different seasons, the temperature
varies from 50 to 100°C, and the relevant chemisorption pressure
is obtained according to Fig. 3.
As for LTS, NH4Cl performs better than NaBr, and both of them
requires small mass, which are only about 31.5–52.4 g per 100 km
and 34.6–57.6 g per 100 km. The mass of BaCl2 is much higher than
the other two LTSs. As for MTSs, CaCl2 and SrCl2 have the similar
performance, and the mass of MTSs is larger than LTSs.
4. Results of composite sorbents-NH3
4.1. Experiments on composite sorbents and comparisons
ð2Þ The development of the composite sorbents for metal halides is
shown in Fig. 4 [24]. Firstly, the sorbent and matrix are both dried
for accurately weighing. After that, the sorbent, matrix and water
are mixed homogenous. And then, the composite sorbent is dried
for the purpose of removing the retained water and the crystal
water. At last the composite sorbent is filled in the sorption reactor
in Fig. 5 and compressed into a block.
The experimental testing device in Fig. 5 consists of a sorption
reactor, an ammonia vessel, a pressure transmitter, a temperature
transmitter and vavles, etc. The temperatures of sorption reactor
and ammonia vessel are controlled by thermostatic oil bath and
cryostat bath. The experimental procedures are as follows:
1386 Z.X. Wang et al. / Applied Thermal Engineering 128 (2018) 1382–1390

Fig. 3. Clapeyron diagram of metal halide-ammonia working pairs.

Table 1
The weight of chemical sorbent per 100 km.

Metal halides Chemisorption Chemisorption Desorption Chemical sorbent Chemical sorbent

temperature (°C) pressure (MPa) temperature (°C) of type-A (g) of type-B (g)
NH4Cl 0 0.223 21.0 31.5–52.4 157.3–262.2
10 0.316
20 0.411
30 0.592
NaBr 0 0141 26.8 34.6–57.6 172.9–288.2
10 0.228
20 0.324
30 0.440
BaCl2 0 0.063 42.0 45.9–76.6 229.7–382.8
10 0.105
20 0.145
30 0.252
CaCl2(8- 0 0.018 60.0–72.0 42.6–71.1 213.2–355.4
2) 10 0.038
20 0.058
30 0.104
SrCl2(8-1) 0 0.015 66.7 44.3–73.8 221.3–368.8
10 0.026
20 0.045
30 0.069

(1) Desorption phase: The pressure is controlled at the 4 bar, oil bath is gradually decreased from 100°C to the lowest
and the sorption reactor is heated by thermostatic oil bath. sorption temperature (about 5°C) with the increment of
The ammonia is desorbed from the sorption reactor and con- 5°C. And then, close the valve and record the relevant data.
densed and collected in the ammonia vessel, and such a pro- Repeat the sorption/desorption process and the accurate
cess is used to instead of the ammonia gas releasing process Clapeyron curves will be obtianed.
in ASS unit. A group of experiments are proceeded with the
sorption reactor temperature ranges from room temperature The cycle sorption quantity is calculated as follows [36]:
(about 25°C) to 100°C, and the increment is 5°C. The valve   
between sorption reactor and ammonia vessel is closed till 1 v 0 ðT e Þ Ae DV
x¼ 1 DðDpÞ þ 00 ð11Þ
the system reaches the equilibrium state. ms v 00 ðT e Þ g v ðT e Þ
(2) Sorption phase: For the ASS unit the ammonia need to be
filled inside the unit after it was used up. In order to inves- where x is the sorption quantity (kg/kg), ms is the sorbent mass (kg),
tigate the performance of ammonia filling process for differ- v0 (Te) and v00 (Te) are the specific volume of saturated liquid ammo-
ent temperatures, open the valve between sorption reactor nia and saturated vapor ammonia (m3/kg) respectively, Ae is the
and ammonia vessel, and the temperature of thermostatic sectional area of ammonia vessel (m2), g is the gravity acceleration
 Z.X. Wang et al. / Applied Thermal Engineering 128 (2018) 1382–1390 1387

Fig. 4. The preparation of composite sorbents. (a1) Drying the sorbent with high temperature, (a2) Drying the granular additive with high temperature, (b) Mixture of granular
sorbent, additive and water, (c) Drying the composite sorbent of sorbent, additive and water with high temperature, (d) Compressing the composite sorbent.

sity of sorbent is 400 kg/m3 with 4:1 of solid sorbent and ENG-TSA,
and the sorption temperature and desorption pressure are 20°C
and 4 bar, respectively [30]. For the data in the Table 2, under
the same experimental conditions, the equilibrium pressure, equi-
librium temperature, and sorption quantity are tested, and then
Clapeyron curves for the experimental data are obtained. The sor-
bent mass of type-A vehicle is calculated by Eq. (5) and the
required ammonia mass is 30–50 g per 100 km. In the same way,
the sorbent mass of type-B vehicle can be obtained.
The result shows that all the composite sorbents have similar
large cycle sorption quantity except BaCl2+ENG-TSA composite
sorbent. According to Table 1, different sorbents adapted to differ-
ent temperature ranges. Thus to find out the optimal and the best-
fit composite sorbent in different areas, weight and bulk volume of
sorbents, local ambient temperature and operating cost for the
whole system need to be taken into account.
Fig. 5. The experimental testing device of sorption/desorption performance of
ammonia.
4.2. Analyses of different composite sorbents

(9.80 m/s2), Dp is the pressure difference between the ammonia
vessel of both sides, D(Dp) is the difference between the sorption/
desorption process data and the initial data (Pa), DV is the ammonia
volume from the valve to the sorption reactor (m3).
In addition, the SEM result of composite CaCl2 [26] (Fig. 6)
shows that the combination of sorbents and matrix is
homogeneous.
Different composite of chemical sorbent with ENG-TSA as
matrix are tested. The cycle sorption quantity and required sorbent
mass of different composite sorbent are shown in Table 2. The den-
As the data shown in Table 1, the minimum weight of chemical
sorbent per 100 km of type-A truck is 31.5 g of NH4Cl per 100 km.
And the maximum weight is 76.6 g of BaCl2 per 100 km. 6.6 kg of
NH4Cl-NH3 working pair (3.4 kg NH4Cl with 3.2 kg NH3) and
13.7 kg of BaCl2-NH3 working pair (8.3 kg BaCl2 with 5.4 kg NH3)
are required for the same 10815.8 km mileage, which are 44.5%
and 73.3% lower than AdBlue.
Generally, the temperature of the truck underframe can reach
50°C during hot summer weather. The pressure in ASS unit
increases as the temperature of sorption bed rises. The pressure
of LTS can goes up to 10 bar under the condition of 50°C, which
is 250% higher than 4 bar. The higher the pressure of LTS is, the
thicker the stainless steel wall of ASS unit is required. Eventually,
it will increase the truck loading. So LTSs are suitable during cold
period or cold area (10°C) because of their low desorption tem-
perature and the low weight of sorbents. And MTSs are more suit-
able for the usual weather which generally more than 10°C.

Table 2
Cycle sorption quantity and the sorbent mass required by different types of trucks per
100 km.

Composite sorbents Cycle sorption Sorbent of Sorbent of

quantity (kg/kg) type-A (g) type-B (g)
NH4Cl+ENG-TSA [30] 0.636 (4 bar) 47.2–78.7 236.0–393.3
NaBr+ENG-TSA 0.704 (4 bar) 42.6–71.0 213.1–355.2
BaCl2+ENG-TSA 0.379 (4 bar) 79.2–132.1 396.2–660.4
CaCl2(8-2)+ENG-TSA [30] 0.613 (4 bar) 49.0–81.6 244.9–408.1
SrCl2+ENG-TSA [30] 0.606 (4 bar) 49.5–82.5 247.6–412.6
Fig. 6. The SEM picture of composite CaCl2 80%, 320 kg m3, 5000 [26].
1388 Z.X. Wang et al. / Applied Thermal Engineering 128 (2018) 1382–1390
Compared with ammonia sorption refrigeration, the diameter of
ASS tank that full of sorbents should be larger, because of the max-
imal ammonia capacity needing and the accurate control of ammo-
nia desorption. Besides, the solid composite sorbent with the mass
ratio of 4:1 was proved with both optimal thermal conductivity
and permeability [34], thus 80% salt with 20% ENG-TSA is selected
for sorbent preparation and sorption/desorption experimental
tests.
4.3. Performance evaluation
The bulk volume and weight of different composite ammonia
sources are compared in Figs. 7 and 8 for type-A truck and type-
B truck. The bulk volume of AdBlue required is:
VA B ¼ VD O  ð3  5%Þ
where VA_B and VD_O are the bulk volume of AdBlue and diesel oil
separately for 100 km mileage.
The bulk volume of composite sorbents can be calculated by
their density and relevant sorbents mass mentioned in Table 2.
Owing to the small emission of NOx pollutant, very small desorp-
tion rate of NH3 is required in a long desorption phase. For example
for type-A truck the required NH3 is only 3–5 kg per 10,000 km. If
the running speed of the truck is 60 km/h, the average desorption
rate is only 0.018–0.03 kg/h. Hence, the influence from the desorp-
tion rate that meets the requirement of NOx releasing rate can be
ignored. Taking one bucket of AdBlue (about 50 L) as a benchmark,
data shown in Figs. 7 and 8 are obtained and compared.
As Figs. 7 and 8 show, the bulk volume and weight of NH4Cl
+ENG-TSA, NaBr+ENG-TSA, CaCl2+ENG-TSA and SrCl2+ENG-TSA
are similar with small differences. The bulk volume of AdBlue
Fig. 7. Bulk volume comparisons of different ammonia sources of two types diesel
vehicles.
Fig. 8. Weight comparisons of different ammonia sources of two types diesel
vehicles.
(Fig. 7) is close to the composite chemical sorbents with small dif-
ferences, but the weight of AdBlue (Fig. 8) is much larger than com-
posite chemical sorbents because of the high density of AdBlue
solution. Additionally, an extra urea pump is needed in a urea-
SCR system. Hence composite metal halides is the optimal choice
for the truck.
On the other hand, the pyrolysis temperature of urea is 160°C.
The urea solution cannot be pyrolysis completely when the
exhaust temperature is lower than 160°C, which results in the
escape of NOx pollutant and the decreasing of average de-NOx
efficiency.
The comparison of NOx conversion rate between composite
sorbent-SCR and urea-SCR is theoretically analyzed in Fig. 9 with
the temperature ranging from 50°C to 250°C. In Fig. 9 the NOx con-
version rate is considered to be the best at NH3/NOx = 0.8–1 [33],
ð12Þ and the de-NOx performance of different catalysts for NH3-SCR
reaction is obtained from reference [28]. For urea-SCR reaction,
the pyrolysis temperature of AdBlue is about 160°C, and NH3 is
generated and reacted with NOx from 160°C. AdBlue is assumed
to be completely pyrolyzed when the temperature reaches up to
250°C, so the de-NOx performance of both urea-SCR and composite
sorbent-SCR is the same when the temperature is higher than
250°C.
The permeability and thermal conductivity of different solid-
state CaCl2 sorption materials are concluded and compared in
Table 3. The sorption/desorption performance of two composite
sorbent (80% CaCl2 and 20% additive) and pure CaCl2 are tested,
with the density of 400 kg/m3. As the experimental data shown
in Table 3, both permeability and thermal conductivity of
CaCl2+ENG-TSA are the highest values, which means the matrix
of ENG-TSA, which has the microporous structure and well-
ordered lamellar structure enhances the heat and mass transfer
performance of CaCl2 significantly [34].
In addition, the NOx conversion effect between composite
sorbent-SCR (take CaCl2+ENG-TSA as composite sorbent) and
urea-SCR at different temperature is presented and compared in
Fig. 9 at a gas hourly space velocity (GHSV) of 30000 ml/(g h).
When NH3: NOx is 1:1 and the oxygen content is 2%, the NOx con-
version rate of the composite sorbent-SCR system is about 45% at
the temperature of 50 °C, but the NOx conversion rate of the
urea-SCR system is zero under the same circumstance. The area
between the composite sorbent-SCR line and the urea-SCR line in
Fig. 9 represents the de-NOx superiority of the composite
sorbent-SCR system at low temperatures, and the area signifies
Fig. 9. Comparison of NOx conversion between composite sorbent-SCR and urea-
SCR.
 Z.X. Wang et al. / Applied Thermal Engineering 128 (2018) 1382–1390
Table 3
Performance comparison among different sorbents with 6 mol/mol cycle sorption quantity.
Solid sorbents Density (kg/m3) Mass ratio of salt and ENG-TSA
CaCl2 [26] 400 1:0
CaCl2+ENG [34] 400 4:1
CaCl2+ENG-TSA [26] 400 4:1
Fig. 10. Different components between (a) composite sorbent-SCR and (b) urea-SCR.
the promotion of the average NOx conversion of the composite
sorbent-SCR system. The ammonia content of the ammonia
sources, the pyrolysis degree of the ammonia contained materials
and the catalytic conversion effect are the major factors for the
NOx conversion results of the NH3-SCR type systems at low
temperatures.
Compared to traditional urea-SCR system, the AdBlue box and
the AdBlue pump are replaced by the ASS unit of composite
sorbent-SCR system, and the locations of the ASS unit in different
diesel vehicles stay the same position with that of AdBlue dosing
system. Small bulk volume and light weight of ASS unit result in
the lighter truck loading and lower diesel oil consumption. So,
the design of the composite sorbent-SCR is significant for the
NOx emission reduction.
Different components of composite sorbent-SCR and urea-SCR
are shown in Fig. 10, and the common parts of which are omitted.
For composite sorbent-SCR, ASS unit consists of stainless steel ASS
tank and the solid sorbents that is saturated with NH3. For urea-
SCR, the corresponding parts of ASS unit are considered to be
AdBlue box, AdBlue solution and AdBlue pump. Taking the bench-
mark in 50 L AdBlue as the example, the AdBlue part includes the
box, pump and AdBlue working fluid. The minimum total price is
4325 CNY, and for which the on-board AdBlue box and pump
occupy 4000 CNY. In comparison, the ASS unit includes the tank,
solid composite sorbent and ammonia. The minimum total price
is 1210 CNY, and for which the on-board ASS tank and composite
sorbent occupy 1030 CNY. The minimum total price for ASS unit
is about 28% of the minimum total price for AdBlue part. For the
utilization of two systems, urea needs much higher heating tem-
perature (above 160°C) than composite sorbent-NH3 (50–100°C),
and composite sorbent-NH3 consumes much less electricity for
heating, which is essential for the initial phase when the trucks
start. Moreover, the theoretical ammonia content of urea is around
18.42% for 32.5% urea solution, while for composite sorbent-SCR
the working media consumed is 100% ammonia, which has lower
price than urea solution.
5. Conclusions
Based on the traditional urea-SCR system for eliminating NOx
emission, with the drawback of low conversion efficiency during
low exhaust temperature, a novel system with composite sorbents
is proposed in this paper. Five kinds of composite sorbents of
1389
Permeability (m2) Thermal conductivity (W/(m K))
16
5.78  10 0.81
8.34  1012 0.89
4.17  1011 15.10
NH4Cl, NaBr, BaCl2, CaCl2 and SrCl2 developed with ENG-TSA as
matrix are studied and analyzed. The conclusions are as follows:
(1) According to the experimental data of different composite
metal halides with ENG-TSA as matrix, BaCl2 composite sor-
bent performs worst, single salt of NH4Cl has the highest
ammonia storage capacity, but NH4Cl and NaBr cannot be
used because of too high working pressure. The ammonia
sorption capacity of CaCl2 and SrCl2 is nearly the same and
has reasonable working pressure, and the CaCl2 is the better
choice for the lower cost compared with SrCl2.
(2) Compared with AdBlue, the finally chosen composite sor-
bent of CaCl2+ENG-TSA performs excellent in smaller bulk
volume, higher utilization ratio of ammonia source (18.42%
ammonia of AdBlue vs. 100% ammonia of ASS), higher NOx
conversion (45% higher than urea-SCR at 50°C), lighter mass,
and lower cost (23.8% of the AdBlue part) of production.
Moreover, the 160°C pyrolysis temperature of AdBlue is
much higher than the desorption temperature of composite
sorbents, which always causes the NOx pollutant escape
from the exhaust pipe, weakens the de-NOx effect, and
requires for higher energy consumption.
(3) In the real application, a wider desorption temperature
range of composite sorbents is desirable for meeting the
reality engineering application. For safety consideration,
more researches on sorbents with low desorption tempera-
ture and low pressure are needed. High temperature salts
(such as MnCl2) blending with other sorption materials
may be a rich research area for this composite sorbent-SCR
system.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China for general program (Grant No. 51576120)
and for Innovative Research Groups (Grant No. 51521004).
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