A Study on Physical Chemistry of Solid A

mmonium Materials for NOx Reduction of

Diesel Engine Emissions

Cheon Seog (Steve) Yoon and Jong Kook Shin

Hannam University, Daejeon, KOREA

Hoyeol Lee and Hongsuk Kim

Korea Institute of Machinery & Materials, Daejeon, KOREA

2014  DOE CLEERS Workshop

University of Michigan, Dearborn, MI, USA

1
 Table of Contents

•  Introduction of Solid SCR System

•  Ammonium Salts
•  Chemical Reactions, Decomposition Chemistry
•  Chemical Kinetic Parameters by TGA, DTA and DSC
•  Decomposition Rate from Hot Plate Test and Chemical Kinetic Parameters
•  Simple Reactor with Visible Window
•  Equilibrium Vapor Pressure Curve for Ammonium Carbonate
•  Acquisition of Re-solidified Materials from Ammonium Carbonate
•  Analytical Study of Re-solidified Materials from Ammonium Carbonate
by XRD, FT-IR, and EA
•  Concluding Remarks
•  Acknowledgement
•  Reference

2
 Solid SCR System

•  NOx purification technology by using NH3, which is generated from solid ammonium.
•  Ammonium carbonate, (NH4)2CO3 , is solid at room temperature, and it
decomposes into NH3, H2O & CO2 above temperature of 60℃.

3
 Material Properties of Ammonium Salts

Solid urea Ammonium carbonate Ammonium cabarmate

Molecular formula (NH2)2CO (NH4)2CO3 NH2COONH4

Molecular weight 60.07 96.09 78.07

Density, g/cm3 1.33 1.5 1.6

Mols NH3 per Mol 2 2 2

Mols NH3 per kg 33.3 20.8 25.6

Decomposition temp., ℃ 140 58 60

NH2CONH2↔ NH3+HNCO
Reaction mechanism (NH4)2CO3↔2NH3+CO2+H2O NH4COONH2 ↔ 2NH3 + CO2
HNCO +H2O ↔ NH3 + CO2

Cost cheap cheap moderate

* HNCO: Isocyanic Acid

[ref] G. Fulks, G. B. Fisher, K. Rahmoeller, M. Wu, and E. D’Herde, SAE 2009-01-0907

4
 Solid Based SCR

Companyny Decomposition Temperature (C

)
Solid Urea Pierburg 140
Ammonia Carbamate FEV + Tenneco 60
Metal Amine* Amminex 32~35
(* Calcium Ammine Chloride, Strontium Ammine Chloride)

5
 Advantage
(Compared with Liquid Urea SCR)
•  ~3 times of ammonia storage capacity

•  Improvement of low temperature NOx conversion performance due to direct am

monia gas injection

•  Enhancement of the reactants mixing characteristics with exhaust gas

6
 Chemical Reactions of Solid Urea

•  Thermal decomposition(pyrolysis) of urea : 19 reactions

(NH2)2CO (s) → NH3 (g) + HNCO (g) for dry urea (140℃~), ΔH298K = 186 kJ
(NH2)2CO (s) + H2O (g) → 2NH3 (g) + CO2 (g) for the presence of water

(NH2)2CO (s) + HNCO (g) → H2N-CO-NH-CO-NH2 (152 ℃ )

H2N-CO-NH-CO-NH2 (g) + HNCO (g) → (HNCO)3 (g) + NH3 (g) (175 ℃)
H2N-CO-NH-CO-NH2 (g) + HNCO (g) → C3H4N4O2(g) + H2O (g) (175 ℃)
HNCO (g) + NH3 (g) → H2O (g) + H2NCN (g) (175 ℃)

•  Hydrolysis of isocyanic acid

HNCO (g) + H2O (g) → NH3 (g) + CO2 (g) , ΔH298K = -96 kJ
- Isocyanic acid is very stable in the gas phase, but hydrolyzes easily on many solid oxides wit
h water vapor originating from the combustion process.

[ref] P.M. Schaber, et al., Thermochimica Acta, Vo. 424, pp 131-142, 2004

7
•  Slow heating for solid urea
- biuret(H2N-CO-NH-CO-NH2), triuret(H2N-CO-NH-CO-NH-CO-NH2 ),
ammonium isocyanate

•  Fast heating for solid urea : NH3, HNCO

Urea
Sublimation
(NH2)2CO
Pyrolysis : + ν
Pyrolysis : + ν
Hydrolysis : + H2O

Ammonia
Cyanuric Acid Isocyanic Acid
NH3
(HNCO)3 HNCO Hydrolysis : + H2O
Pyrolysis : + ν

[ref] M. Kobel and E.O. Strutz, Ind. Eng. Chem, Res. Vol. 42, No. 10. pp 2093-2100, 2003

8
 Decomposition Chemistry of Ammonium
Carbamate and Ammonium Carbonate (1/2)
•  Ammonium carbamate [NH4COONH2], ammonium carbonate [(NH4)2CO3
]
NH4COONH2 (s) ↔ 2NH3 (g) + CO2 (g)
(NH4)2CO3 (s) ↔ 2NH3 (g) + CO2 (g) + H2O (g)

•  Ammonium carbamate [NH4COONH2] : 2 steps, carbamic acid (unstable in

termediate, HCOONH2 )
NH4COONH2 (s) ↔ NH3 (g) + HCOONH2 (g)
HCOONH2 (g) ↔ NH3 (g) + CO2 (g)

•  Ammonium carbonate [(NH4)2CO3 ] : 2 steps, ammonium bicarbonate (sta

ble intermediate, (NH4)HCO3 )
(NH4)2CO3 (s) ↔ NH3 (g) + (NH4)HCO3 (g)
(NH )HCO (g) ↔ NH (g) + CO (g) + H O (g)
[ref] J. E. House,4 Jr., “A TG
3 study of the kinetics
3 of decomposition
2 of ammonium
2 carbonate and ammonium bicarbonate, ” Thermochimica Acta, 40,
225-233, 1980

9
 Decomposition Chemistry of Ammonium
Carbamate and Ammonium Carbonate (2/2)
•  Commercially available ammonium carbonate : ammonium carbamate + a
mmonium bicarbonate [(NH4)2CO3 ]

heating
•  Ammonium carbamate urea (NH2CONH2) is byproduct
NH4COONH2 (s) ↔ NH2CONH2 (g) + H2O (g)

•  @ high temperature, urea isocyanic acid [HNCO], NH3

NH2CONH2 ↔ NH3 (g) + HNCO (g)
HNCO + H2O ↔ NH3 (g) + CO2 (g)

•  Cycles of heating and cooling processes during the vehicle operation mixt
ure of ammonium carbamate, ammonium carbonate, ammonium bicarbonat
e, and urea are existed.
[ref] C. B. Sclar and L. C. Carrisonm “Phase composition of commercial ammonium carbonate,” Science, Vol. 14, pp. 1205-1207, 1963
[ref] B. R. Rahachandran, A. M. Halpern, and E. D. Glendening, “Kinetics and mechanism of the reversible dissociation of ammonium carbamate:
involvement of carbamic acid,” J. Phys. Chem. A, 102, 3934-3941, 1998

10
 Decomposition Characteristics of Solid Urea (1/2)

By-product substance formed from heating and cooling process of

solid urea

•  Biuret and isocyanic acid can be formed in the process of thermal decomposition.
•  It decomposes to ammonia at high temperatures of 200 ∼ 300℃.
•  It is one of limitations for the practical use of solid urea.
[ref] H. Kim, C. S. Yoon, J. Lee, and H. Lee, SAE 2014-01-1535

11
Decomposition Characteristics of Solid Urea (2/2)

Dosing valve clogging when abnormal temperature control of the solid urea system

•  Heating up the dosing module with high temperatures to prevent clogging is

another difficulty for solid urea system.

[ref] H. Kim, C. S. Yoon, J. Lee, and H. Lee, SAE 2014-01-1535

12
Hot Plate Experiment (Device)

plate supporter

plate

heater

13
Chemical Kinetic Parameters and Decomposition
Rate of Solid Urea
- Chemical kinetic parameters(activation energy and frequency
factor) of solid urea (TGA Q500 used) 4 step reactions
Activation Energy(E) Frequency factor(A)
Step
kJ/mol s-1

Step 1-1 64.26 2.2.E+04

Step 1-2 40.85 2.3.E+01

Step 2 65.64 1.5.E+03

< TGA graph for solid ure >
Step 3 128.14 1.3.E+08

- Decomposition rate of solid urea in hot plate experiment

Temperature Decomposition rate

℃ %/min

173 0.53

198 12.23

230 16.88

240 20.39

255 29.15
< Comparison of decomposition rate for solid urea in
273 35.06 hot plate experiment and TGA analysis >

14
Chemical Kinetic Parameters and Decomposition
Rate of Ammonium Carbonate
- Chemical kinetic parameters(activation energy and frequency
factor) of ammonium carbonate(TGA Q500 used)

1 STEP
Range(α) 1 step reaction
E(kJ/mole) A(s-1)

α = 0.04 - 0.5 62.22±5.76 4.23.E+06 

α = 0.04 - 0.8 53.40±5.67 1.75.E+05

α= (mo-mt)/mo
< TGA graph for ammonium carbonate >

- Decomposition rate of ammonium carbonate in hot plate

experiment

Temperature(℃) %/min

75 15.83

85 19.13

95 28.43

105 33.62

115 36
< Comparison of decomposition rate for ammonium
carbonate >

15
Chemical Kinetic Parameters and Decomposition
Rate of Ammonium Carbamate
- Chemical kinetic parameters(activation energy and frequency
factor) of ammonium carbamate(TGA Q500 used)

1 STEP
Range(α) 1 step reaction
E(kJ/mole) A(s-1)

α = 0.04 - 0.5 57.22±4.10 1.48E+06 

α = 0.04 - 0.8 49.41±3.77 7.84E+04 

α= (mo-mt)/mo < TGA graph for ammonium carbamate >

- Decomposition rate of ammonium carbamate in hot plate

experiment

Temperature(℃) %/min

64 5.68

74 9.01

84 15.46

90 21.8

97 27.14
< Comparison of decomposition rate for ammonium
110 47.65 carbamate >

16
 Calculations of Chemical Kinetic Parameters for
DSC Results of Ammonium Carbonate
•  By Kissinger method

Tm
Kissinger method

Activation energy(E) Frequency factor(A)

Ammonia salt
kJ/mol s-1

Ammonium carbonate 75.49 6.254 × 107

17
 Calculations of Chemical Kinetic Parameters for
DSC Results of Ammonium Carbamate
•  By Kissinger method

Tm
Kissinger method

Activation energy(E) Frequency factor(A)

Ammonia salt
kJ/mol s-1

Ammonium carbamate 67.96 1.159 × 108

18
 Comparison of Activation Energy

•  Validation
Activation energy(E)(kJ/mol)
 
Paper DSC TGA-a TGA-b

Ammonium carbonate 86.73±6.02 1) 75.49 62.22±5.76 53.40±5.67

Ammonium carbamate 53.59 2) 69.96 57.22±4.10 49.41±3.77

* a(α = 0.04~0.5), b(α = 0.04 ~ 0.8)
α= (mo-mt)/mo

Activation energy(E) : Ammonium carbonate > Ammonium carbamate

1) J. E. House, Jr., “A TG study of the kinetics of decomposition of ammonium carbonate and ammonium bicarbonate, ” Thermochimica Acta, 40, 225-233,
1980

2) B. R. Rahachandran, A. M. Halpern, and E. D. Glendening, “Kinetics and mechanism of the reversible dissociation of ammonium carbamate:
involvement of carbamic acid,” J. Phys. Chem. A, 102, 3934-3941. 1998

19
Equilibrium Vapor Pressure of Ammonium Carb
onate

Pressure sensor

Pressure vessel
Heater controller

Heater

Minimum temperature is required for reactor and dosing

device

20
 Simple Reactor with Visible Window
T/C Pressure Sensor

Heater

Visible window
Heater controller
< Test conditions for reactor temperature and pressure with ac-1 >

ac-1

Closed vessel Visible window Resolidification materials

around cooling pipe in the reactor

ac-2

< Test conditions for three cycles of heating and cooling with ac-2 >
Closed vessel Inside of reactor after 12 hours

21
 XRD Analysis of Re-solidified Materials from A
mmonium Carbonate
•  Sample (ac-1) : around the cooling pipe in the reactor
•  Sample (ac-2) : inside of the reactor after 3 times of heating & cooling cycles.

- XRD peak : 29.68˚, 23.9 ˚, 30.92 ˚, 24.45 ˚, 31.03 ˚, 36.43 ˚

< XRD spectra of ac-1, ac-2, ammonium carbonate,

ammonium carbamate, and solid urea standards >

Re-solidified samples (ac-1 & ac-2) have similar patterns of XRD peak with pure ammonium
carbonate.

22
 XRD Summary Data of Re-solidified Materials f
rom Ammonium Carbonate
Standard 2θ
(deg)
d
(spacing-Å
Relative
Intensity(%)
•  XRD summary Data(wavelength 1.54056Å)
)
Ammonium 29.6 3.01 100
carbonate[1]
23.4 3.74 49.7
34.4 2.6 42.8
Ammonium 29.68 3.002 100
•  XRD Bragg’s Law
bicarbonate
23.9 3.669 37.1
30.92 2.893 17.0
ac-1 29.76 2.995 100
23.87 3.674 69
26.22 3.365 54.1
ac-2 29.72 2.999 100
23.87 3.674 48.7
26.19 3.368 37.8
Ammonium 30.32 2.945 100
carbamate
32.37 2.777 15.82
19.53 4.447 11.41
Solid urea 22.26 3.924 100
[ref] 1. Analytical Chemistry. 2005, 77, 5947-5952
35.44 2.564 17.75
2. “Phase Composition of Commercial Ammonium Carbonate”, Science 14(1963), 1205-1207
36.96 2.474 9.43
23
 FT-IR Analysis of Re-solidified Materials from
Ammonium Carbonate
•  Sample (ac-1) : around the cooling pipe in the reactor
•  Sample (ac-2) : inside of the reactor after 3 times of heating & cooling cycles.

1300 ~ 1600 cm-1 bands : CO group of carbonate ion

3033 cm-1 bands : group of ammonium ion

< FT-IR spectra of ac-1, ac-2, ammonium carbonate,

ammonium carbamate, and solid urea standards >

Re-solidified samples (ac-1 & ac-2) have similar patterns of FT-IR spectra with pure
ammonium carbonate.

24
EA(Elemental Analyzer) Analysis of Re-solidified
Materials from Ammonium Carbonate
EA summary data (detection limit 0.05%)
Sample Standard Element(%)

Nitrogen 25.34

Ammonium carbonate Carbon 15.39

Hydrogen 7.54

Nitrogen 34.98

Ammonium carbamate Carbon 14.80 𝐶=​12.01/79.06 𝑋+X=79.06(

​12.01/96.09
​2𝐶/12.01
 Y  −
Hydrogen 8.18

N=​14.01/79.06 𝑋+
Y​28.02/96.09
=96.09(  Y  −
​𝑁/14.01
Nitrogen 17.43
Ammonium
Carbon 15.22
bicarbonate
Hydrogen 6.88

Nitrogen 17.76

ac - 1 Carbon 15.50 •  ac-1 is similar to ammonium bicarbonate.

Hydrogen 6.66
•  ac-2 is similar to mixture of ammonium
Nitrogen 16.87

ac - 2 Carbon 13.29 carbonate and ammonium bicarbonate

Hydrogen 5.69

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 Concluding Remarks (1/2)

Basic research on reaction rate of solid urea, ammonium carbonate, and ammonium car
bamate as ammonia sources for the application of solid SCR was performed

•  Chemical kinetic parameters(activation energy and pre-exponential factor) are calcu

lated by Arrhenius plot from TGA and DSC results using Kissinger method.

•  From this study, activation energy of ammonium carbonate is larger than that of am
monium carbamate.

•  Decomposition rate from chemical kinetic parameters by TGA for solid urea, ammo
nium carbonate, and ammonium carbamate, and that of hot plate experiment do not
have discrepancies each other.

26
 Concluding Remarks (2/2)

Analytical study of re-solidified materials from ammonium carbonate was carried out.

•  Simple reactor which has heater control and temperature control of cooling water w
ith visible window was designed and fabricated, pressures and temperatures are mea
sured.

•  Saturation pressure curve as function of temperature was obtained and governed for
the design of reactor and dosing system.

•  Re-solidified materials of ammonium carbonate from heating and cooling cycles are
very similar to original materials of ammonium carbonate and ammonium bicarbon
ate from analytical results by XRD, FT-IR, and EA.

27
 Acknowledgments

•  This research was supported by the Center for Environmentally Friendly V

ehicle (CFEV) as a Global-Top Project of the Ministry of Environment, Ko
rea (KMOE)

28
 Reference

•  G. Fulks, G. B. Fisher, K. Rahmoeller, M. Wu, and E. D’Herde, “A Review of Solid Materials

as Alternative Ammonia Sources for Lean NOx Reduction with SCR,” SAE 2009-01-0907, 2
009.
•  C. B. Sclar and L. C. Carrison, “Phase Composition of Commercial Ammonium Carbonate,”
Science, Vol. 14, pp. 1205-1207, 1963.

•  H. Lee, C. S. Yoon, and H. Kim, “A Study on Reaction Rate of Solid SCR for NOx Reduction
of Exhaust Emissions in Diesel Engine,” Transaction of KSAE, Vol. 21, No. 6, pp. 183-194,
2013.
•  J. K. Shin, H. Lee, C. S. Yoon, and H. Kim, “Analytical Study on Re-solidification Materials(
Ammonium Carbonate Intermediates) for NOx Reduction of Exhaust Emissions in Diesel Eng
ine with Solid SCR,” Transaction of KSAE, Vol. 22, No. 4, pp. 151-159, 2014.
•  H. Kim, C. S. Yoon, J. Lee, and H. Lee, “A Study on the Solid Ammonium SCR System for C
ontrol of Diesel NOx Emissions,” SAE 2014-01-1535, 2014.

29
Thank you for your attention !

Cheon Seog Yoon (csyoon@hnu.kr)

Professor, Ph.D.
Department of Mechanical Engineering
Hannam University
Daejeon, KOREA

30
70 kW Off-Road Vehicle (Tractor)

◈ Specification of engine

Bore x Stroke(mm) 98 x 113

No. of Cylinder 4
Displacement(cc) 3,409
Comp. Ratio 18.5
Valve per cylinder 4(2 Intake, 2 Exhaust)
Firing order 1-3-4-2
Combustion System Direct Injection
Aspiration Turbocharged
Max. Power 80PS @ 2500rpm
Injection pressure 80 MPa

31
 Re-solidification of Ammonium Carbonate

Visible  window

Re-­‐solidified  material

Electric  heater

Ammoium  Carbonate (a) Four different test conditions

Pressure  vessel
A B C D
Schematic diagram of a simple reactor with a
visible window having a pipe (cooling water
flow through the pipe)

(b) Photos of visual windows for different conditions

☞ Re-solidified materials were observed under the temperature of vapor pressure curve.
[ref] H. Kim, C. S. Yoon, J. Lee, and H. Lee, SAE 2014-01-1535

32