Recent research on combustion and NOx reduction at Donghua University

2016/6/16
1
Recent research on
combustion and NOx reduction
at Donghua University
Dr. Prof. Yaxin Su
School of Environmental Science and Engineering,
Donghua University
2016.6.24
Report at Institute of Chemical Processing of Coal, Poland, 2016.6.24
1. Introduction
 Before going to the academic topics, I’d
like to show you where Donghua
University locates and what Donghua
looks like.

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1.1 Location of Shanghai in China
Qinlin Moutains-Huaihe River
Changjiang River
1.2a City view of Shanghai

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1.2b City view of Shanghai
492m,2008
632m,2016.3.12
420.5m,1999
1.2c City view of Shanghai

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4
1.2d City view of Shanghai
 The 1st maglev train in the world
Max Speed:430 km/h,
Length: 29.863 km
Run since 2002.12.31
From Pudong
International airport
to the Metro Line 2
at Longyang Road
1.3 Some basic data of Shanghai
 Shanghai covers about 6340 km2 with a population 24.1527 millions (2015)
 GDP per capita is 103100 CNY, about 14900 US $( 2015)
 Human Development Index is 0.9
 Metro line: 617km
 2 Airport, 3 main railway stations and 6 minor railway stations
 GDP: No. 1 in China and No. 2 in Asia (2014)
 Shanghai port cargo handling capacity and container throughput : No. 1 in the
world in 2014
 41 universities and 25 colleges
 59 Institutions authorized to provide graduate degrees (MS, PhD)

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1.4 Location of Donghua University in Shanghai
PVG
airport
1.4a Yan’an Road campus
Metro
Line 3/4North
North
Entrance
Our school
before 2005

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1.4b Pictures of Yan’an Road Campus
1.4c Songjiang Campus ( School of ES&E)
North
East
Entrance
North
Entrance
School of
ES&E

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1.4d Pictures of Songjiang Campus
1.5 History of Donghua University
 Donghua University (DHU was founded in 1951,known firstly as
East China Institute of Textile Technology , then China Textile
University (1985-), then Donghua University (1999-)
 DHU is now a multi-disciplinary university, including engineering,
economics, management, literature and art, laws, science, and
education.
 12 colleges and schools, offering 54 undergraduate programs, 59
master’s degree programs, 30 doctoral degree programs.
 more than 2,800 faculty and staff,
 and over 30,000 enrolled students, among which about 4000
oversea students and 6000 graduate students.
 Top 1 in the field of textile, fiber materials and fashion in China and
comprehensively ranked the 50th among all the universities in China.

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History of Donghua University
Back
A video by an International
student—Shanghai in my eyes
 http://english.dhu.edu.cn/_s126/7b/dd/c51
78a97245/page.psp

2016/6/16
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2. Combustion related research:
Completed and going-on
 CFB combustion
 Desulfur, deNOx model in furnace;
 Heat transfer in furnace;
 Cyclone separator;
 HiTAC( High Temperature Air Combustion)
 Multi-jet burners;
 Swirling burners;
 NOx reduction
 by reburning
 Mixed fuels based on common wastes, e.g., tires, biomass and lignite ash,
biomass ash and iron oxides;
 by HC, like CH4,C2H6,C3H8,etc, over iron/iron oxides
 by HC over iron-based supported catalysts
 CO2 capture
 Sludge pyrolysis and combustion
2.1.1 High Temperature Air Combustion (HiTAC)
 Also known as MILD(Moderate and Intensive Low-oxygen Dilution),
Flameless Oxidation – FLOX
 Advantages:
 Significantly increased thermal efficiency by recovering the heat
from exhaust flue gases with regenerative system to preheat the
combsution air to , e.g., above 1000 C;
 Very low NO emission by controlling the O2 in preheated air, e.g.,
as low as 2%-5 vol. %;
 methods of realization of HiTAC
 Burners- the most important device;
 Support combustion with low O2
 Regenerative system: ceramic honeycomb
 Recover waste heat from flue gas
For industrial application and furnace design, the jet parameters and burner
configuration are very critical for a good combustion in the furnace.

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2.1.2 Burners of HiTAC
 Basically, two types of burners used in industry
a. the combustion air is provided by a central, strong (high-momentum)
air jet that is surrounded by a number of weak (low-momentum) fuel
jets (in industrial applications typically two jets are used).
b. a central fuel jet and a number of air jets positioned in the relative
vicinity of the central fuel jet—recognized in the literature as a
“classical” method of achieving flameless combustion
Fuel jet
Preheated air
jet
2.1.3 Burners developed in our lab
 Multi-jets burner
 Swirling burner
furnace
Swirling burner
fuel
air

air
fuel
Multi-jets burners
one circular fuel jet in the center surrounded
by 5 circular air jets distributed equably
according to the air straddle angle,  , an
inclined angle of the fuel jet, 
D
L

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2.1.4 Numerical simulation based CFD- Multi-jets burners
 gas combustion:
 standard k- model + -PDF combustion model;
 Radiation:
 Discrete Ordinates method;
 NOx model:
 thermal + prompt NOx model;
 Code: FLUENT
Local O2 ,Temperature and NO field in the furnace (Tair=1273K, Tfuel=300K,
=30, =120 , L/D=2.5, vf/vair=1.18, O2=10%,15%, 21% )
8 10 12 14 16 18 20 22
0
50
100
150
200
250
300
350
Tair
=1273K, Tfuel
=300K
=30
o
, =120
o
vf
/vair
=1.18, L/D=2.5
NOxemission/ppm
O2
fraction in preheated air / %
2.0 2.2 2.4 2.6 2.8 3.0
40
50
60
70
80
90
100
Tair
=1273K, Tfuel
=300K
=30
o
, =120
o
O2
=15%, vf
/vair
=1.18
NOemission/ppm
L/D

air
fuel
Multi-jets burners
D
L
2.1.5 Numerical simulation based CFD-swirling burners
 gas combustion:
 Reynolds Stress model + -PDF combustion model;
 Radiation:
 Discrete Ordinates method;
 NOx model:
 thermal + prompt NOx model;
 Code: FLUENT
Direction
injection
burner
Swirling
burner
Flow vector temperature O2 distribution NO distribution
Air inlet Max. Temp.
(K)
Avg. Temp.
(K)
CO molar
fraction(ppm)
NO molar
fraction(ppm)
Direct injection (=0) 1876 1575 372 35.2
Swirling (=180) 1914 1633 29 12.3
Swirling burner results to better combustion: better mixing of fuel and air, lower local O2 concentration and thus
lower local NO formation, better burnout of fuel and higher temperature in the furnace.

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2.1.6 Papers and patents on HTAC
 2 China patents authorized;
 10 Chinese Journal papers;
 12 International Conference proceeding papers;
2.2 NOx reduction
Typical NO
reduction
methods
Post-combustion
Selective catalytic reduction (SCR)
Selective non-catalytic reduction (SNCR)
Reducing agent: NH3
Efficiency high,
but expensive
Combustion
modification
Low excess air: OFA
Low NOX burner (LNB)
Flue gas re-circulation (FGR)
Efficiency
low
Reburning <60%
Because of HCN/NH3(coal, NG)
Char-N (coal)
reduced by Fe2O3
Catalyst (e.g., V2O5TiO2) +reducing agent (NH3)

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2.2 our recent work on NOx reduction
We did the following researches on NO reduction since 2010.
 by reburning
 Mixed fuels based on common wastes, e.g., tires, biomass and
lignite ash, biomass ash and iron oxides;
 by HC, e.g., CH4,C2H6,C3H8,etc, over iron/iron oxides
 by HC over iron-based supported catalysts
2.2.1 Background of Reburning
 “In-Furnace-Control” of NOX:
- Create a fuel rich zone/stage.
- Chemically reduce the NO to N2.
 Discovered in 1973 in the US.
 First used in Japan in 1983 – 50%
reduction in NO realized.
 First used in China in 2001– also 50%
reduction in NO realized.

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2.2.2a Natural Gas Reburning
 C-, CH- and CH2-, effectively
reduce NO to HCN, then HCN to
N2 via extended Zelidovich
mechanism
 A problem is that HCN oxidizes to
NO in the burnout zone,
 Thus, there is a 60% NO
reduction floor.
2.2.2b Coal Reburning
 Char is the major reaction
intermediate which contains
nitrogen,
 Char nitrogen oxidizes to
NO in the burnout zone,
 Thus, there is also a 60%
NO reduction floor.

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2.2.3 Previous Results
Use of Lignite Fly Ash to Reduce HCN during Methane Reburning
 Bag-house ashes are more effective at HCN reduction than those from an
electrostatic precipitator, they are also effective at NH3 reduction.
W-YChen and B B Gathitu,
Fuel, 2009, 85:1781-1793
2.2.4a Drawbacks of using Lignite Fly Ash for HCN Reduction
 The amounts of fly ash required are impractical (720
metric tons per day for a 172 MW coal-fired utility boiler).

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2.2.4b Substitutes Lignite Fly Ash
 Substitute for lignite fly ash:
 Required quantities should be reasonable.
 It should not impact boiler performance adversely i.e.
slagging and fouling.
 Iron oxides selected as lignite fly ash substitute
after critical review of literature.
2.2.5 NOx reduction by mixed fuels Reburning
 We proposed mixed fuels based on several widely
available wastes and demonstrated a NO reduction
efficiency of more than 85% after burnout, which
made it more competitive than currently preferred
technologies such as SCR.
 The major contribution is that a method to control
reburning intermediates, HCN/NH3 was recognized.

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2.2.5 Effectiveness of Fe2O3 at HCN Reduction
 Due to long residence time in our reactor, HCN thermal
decomposes.
 Fe2O3 effectively converts HCN over a wide range of temperatures.
HCN Concentration in Helium = 600 ppm
Fe Concentration = 1200 ppm
Residence Time = 0.2 sec
0
50
100
150
200
250
300
350
1100 1150 1200 1250 1300 1350
Furnace Temperature (°C)
ExitHCN(ppm)
HCN Yields Without Fe2O3 HCN Yields With Fe2O3
Su, Y X, et al, Fuel,
2010, 89:2569-2582
2.2.6 Mechanism of HCN reduction by Fe2O3
Fe2O3+3CO2Fe+3CO2
2Fe+3NOFe2O3+1.5N2
2Fe2O3+3HCN4Fe+3CO+3NO+1.5H2

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2.2.7 Effects of Water and Temperature during
Reburning and Burnout with Fe2O3
 Presence of water vapor and high temperatures enhance its activity.
 Temperature of 1250 °C is selected because thermal decomposition is minimal
and activity of Fe2O3 present
 Water concentration of 6.35% selected – typical to that in coal-fired boilers.
SR2 = 0.85, SR3 = 1.1
Feed NO = 500ppm
Burnout Furnace Temperature = 1150 °C
45%
50%
55%
60%
65%
70%
75%
80%
0 1000 2000 3000 4000 5000
Fe Concentration (ppm)
NominalNOReduction(%)
1250 °C (without water) 1250 °C (with 6.35% water)
1250 °C (with 17% water) 1150 °C (with 6.35% water)
2010, 89:2569-2582
2.2.8a NO Reduction by Mixed Reburning Fuels
 With a temperature and water concentration selected, other fuels
were tested at optimal SR2 for NO reduction and optimal SR3 to
achieve burnout
Feed NO = 500ppm
Furnace Temperatures: Reburn = 1250 °C, Burnout = 1150 °C
40%
45%
50%
55%
60%
65%
70%
75%
80%
85%
90%
0 1000 2000 3000 4000 5000 6000 7000 8000
Chinese Tire (SR2 = 0.9, SR3 = 1.2) Pine Bark SR2 = 0.9, SR3 = 1.3)
Corn Stover Residue (SR2 = 0.9, SR3 = 1.25) Sludge (SR2 = 0.95, SR3 = 1.3)
Wood Fines (SR2 = 0.9, SR3 = 1.3) US Tire (SR2 = 0.9, SR3 = 1.2)
Methane (SR2 = 0.9, SR3 = 1.1)
 A combination of
material A and F form an
excellent substitute for
natural gas and lignite
ash.
 Up to 88% NO reduction
possible at 4000ppm of
Fe2O3 (185 metric tons
per day for a 172 MW
coal-fired boiler –
compared to 720 metric
tons of lignite fly ash)
 Char-N conversion to NO
in the burnout zone limits
the other fuels.
 Fe2O3 does not cause
fouling or slagging in the
boiler.
2010, 89:2569-2582

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2.2.8b NO Reduction by Mixed Reburning Fuels
Feed NO = 500ppm
Furnace Temperatures: Reburn = 1250 °C, Burnout = 1150 °C
60%
65%
70%
75%
80%
85%
90%
0 1000 2000 3000 4000 5000 6000 7000 8000
Chinese Tire with Mill Scale (SR2 = 0.9, SR3 = 1.2) Methane with Mill Scale (SR2 = 0.9, SR3 = 1.1)
Chinese Tire with Sea Nodules (SR2 = 0.9, SR3 = 1.2) Methane with Sea Nodules (SR2 = 0.9, SR3 = 1.1)
Effects of mill scale and sea nodules on NO reduction efficiencies of tire and
methane as reburning fuels during two-stage tests.
A mixture of tire and
mill scale can achieve
up to 82% NO
reduction, while tire
and sea nodules can
achieve 78% NO
reduction.
Mill scale contains 90
% Fe2O3 while sea
nodules contain only
20% Fe2O3 making mill
scale the better option.
2010, 89:2569-2582
 At present, there is a great incentive to use natural gas or other
hydrocarbons as reductant in stationary SCR units rather than
NH3, because of:
 In many new power plants, NG is commonly used as fuel
and is readily available;
 NH3 is more expensive, requires special handling and
storage and needs a sophisticated metering system to avoid
NH3 slip.
 We recently experimentally demonstrated that methane could
effectively reduce NO over iron/ iron oxides.
2.3 NOx reduction by iron with HC

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2.3.1 First work on NO reduction by iron
B. Gradon & J. Lasek，Fuel 89 (2010) 3505–3509
NO molar fractions measured in the gas leaving the reactor in
function of time: temperature 850 C, gas mixture 1015 ppm
NO/N2, four iron samples of surface area 1.2110-3 m2, gas
stream 9.54 10-4 mol/s.
Influence of vary oxygen molar fractions in the
reacting gas on the NO reduction efficiency at
temperature 850 C and average iron surface area
1.16  10-3 m2.
Iron ball of diameter
of 10mm as iron
sample
We continued and
improved the work.
2.3.2 our further work--Experimental setup
Length
Width
6mm6mm
Iron mesh Mesh roll
Fig. 2 Iron mesh roll
Iron mesh roll
Electrically
heat furnace
Reactor
tube
Simulated
flue gas
To analyzer
Fig 1 Experimental setup
simulated flue gas consisting
0.05% NO in nitrogen base,
flow rate:1.5 L/min
ceramic tube of inner
diameter of 2.5 cm
online analyzer
(ECOM-J2KN,
Germany)
iron mesh size
160mm×80mm
80mm×80mm
160mm×40mm
Reacting time
0.13s
0.13s
0.06s

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2.3.3 Results and discussion
 2.1 Reduction of NO by iron.
20
40
60
80
100
300 600 900 1200
temperature (°C)
Efficiency(%)
160mm x 80mm
80mm x 80mm
160mm x 40mm
Reacting time
0.13s
0.13s
0.06s
4 0 5 0 6 0 7 0 8 0 9 0
0
5 0 0
1 0 0 0
1 5 0 0
2 0 0 0
T w o - T h eta ( d e g )
F e
F e ,N i
XRD results of the original iron
XRD results of the iron after reaction with NO
in N2 atmosphere (1100 C)
3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0 1 1 0 1 2 0
0
5 0 0
1 0 0 0
1 5 0 0
2 0 0 0
2 5 0 0
T w o -T h e ta (d e g )
F e
F e + 2 F e2 + 3 O 4
F e 2 O 3
2x yFe NO Fe O N  
 2.3.3.1 Reduction of NO by iron
0 10 20 30 40 50 60 70
20
40
60
80
100
NOreduction/%
durable time /hr
durable reduction of NO by metallic iron in N2 atmosphere
(flow rate 1.5L/min, NO=0.05in N2 base at 800 C)
10 20 30 40 50 60 70 80 90
0
500
1000
1500
2000
 Fe2O3

 Fe
+2
Fe2
+3
O4
  




















 
Intensity(CPS)
2()
XRD pattern of iron oxides after durable reaction
Fe could reduce NO to N2, while it is oxidized to FexOy( finally Fe2O3), resulting to decreased NO
reduction. Therefore, a reducing agent should be added to reduce iron oxides to iron in order to
keep the reaction.
CO and CH4 were used as reducing agents and NO reduction was tested respectively in simulated
flue gas. The iron oxides after the above durable test was used as iron oxides in the following test.

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 2. 3.3.2 Reduction of NO by iron + CO/CH4
0
20
40
60
80
100
0 20 40 60 80 100
durable time, hr
NOreduction,%
stop CO and feed 1.17% CH4
Durable reaction of NO reduction by CO/CH4 over iron oxides in
simulated flue gas (O2: 2.0%, CO2: 16.8%, NO: 524ppm in N2
base) at 1000 C
10 20 30 40 50 60 70 80 90
0
500
1000
1500
2000
2500
3000
3500
FeO
+ Fe
+2
Fe2
+3
O4
+
+
++
++
+
+
+
+
++
+
Intensity(CPS)
2()
+
XRD pattern of iron oxides after durable reaction
with CH4 and NO at 1000 C
Very good NO reduction when CH4 was used as reducing agent over iron oxides. Iron oxides( Fe2O3) was partly
reduced ( Fe3+ Fe2+)
Further test was conducted in N2 atmosphere to find out the mechanism.
 2.3.3.2 Reduction of NO by CH4 over iron oxides
2 0 0 3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 8 0 0 9 0 0 1 0 0 0 1 1 0 0
0
2 0
4 0
6 0
8 0
1 0 0
NOreduction/%
T e m p e r a t u r e / ℃
NO reduction by methane over iron oxides
(flow rate 1.5L/min, CH4=1.17%, NO=0.05% in N2 base)
200 300 400 500 600 700 800 900 1000 1100
0
1000
2000
3000
4000
5000
6000
ExitCO/ppm
Temperature/℃
C H 4
=1.17%
CO formation
(flow rate 1.5L/min, CH4=1.17%, NO=0.05% in N2 base)
10 20 30 40 50 60 70 80 90
0
200
400
600
800
1000
6
88
6


8


6

8
8

8 FeO
6 Fe
Fe2O3
 Fe
+2
Fe2
+3
O4
Intensity(CPS)
2()


XRD pattern of iron oxides after reaction
(flow rate 1.5L/min, CH4=1.17%, NO=0.05% in N2 base, 1050C)
SEM image of iron oxides after reaction
(flow rate 1.5L/min, CH4=1.17%, NO=0.05% in N2 base, 1050C)
CO formed
Iron oxides reduced to iron
Carbon formed

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 2.3.3.3 mechanism of NO reduction by methane over iron oxides
 The mechanism was rather complex and includes the following
paths:
 NO reduction by methane via reburning
 Iron oxides reduction to iron by methane
 NO reduction by iron
 NO reduction by methane via reburning
In fuel rich conditions, methane could reduce NO through reburning mechanism with the following basic route
 HCNNOCHi （R1）
Then HCN was reduced to N2 according to the extended reverse Zeldovich reactions:
HNCOOHCN 
CONHHNCO 
2HNHNH 
ONNON 2 
(R2)
(R3)
(R4)
(R5)
Fe2O3 could reduce HCN:
2 3 2 23 2 3 1.5 1.5Fe O HCN Fe CO N H     R(6)
Discussion:
Reburning needs O radical, as showed in (R2).
Iron oxides could provide lattice oxygen to make
reburning happen. However, in N2 atmosphere, O
radical provided by iron oxides is not enough to
make reburning the dominant mechanism.
However, in real condition where there is O2 in
the flue gas, reburning happens.

2016/6/16
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-600
-500
-400
-300
-200
-100
0
100
200
300
300 500 700 900
Temperature/ o
C
△G
R10 R11 R12
R13 R14 R15
The lattice oxygen provided by iron oxides (Fe2O3 and Fe3O4) at high temperature could partially oxidize methane to
CO/CO2 and the iron oxides would be reduced to metallic iron at the same time by methane above 570 C according to
the sequence Fe2O3 Fe3O4 FeOFe.
Main reactions:
2 3 4 3 4 23 ( ) 2 ( ) 2 ( )Fe O CH g Fe O CO g H g   
3 4 4 2( ) 3 ( ) 2 ( )Fe O CH g FeO CO g H g   
4 2( ) ( ) 2 ( )FeO CH g Fe CO g H g   
(R10)
(R(11)
(R12)
Secondary reactions:
2 3 4 3 4 2 212 ( ) 8 ( ) 2 ( )Fe O CH g Fe O CO g H O g   
3 4 4 2 24 ( ) 12 ( ) 2 ( )Fe O CH g FeO CO g H O g   
4 2 24 ( ) 4 ( ) 2 ( )FeO CH g Fe CO g H O g   
(R13)
(R(14)
(R15)
100
150
200
250
300
350
400
450
500
300 500 700 900
Temperature/
o
C
△H
R10 R11 R12
R13 R14 R15
changes of the thermodynamics Gibbs free energy, G, and the reaction heat, H
1
2
3
CO formed
during the
reaction of iron
oxides with
methane. CO
/H2 will further
react with iron
oxides and
reduce iron
oxides to iron.
 In addition, methane will decompose to C and H2 at high temperature:
4 2( ) 2 ( )CH g C H g 
The cracking reaction of methane begins at 550C, but it goes on
very slowly at 600-850 C and no more than 3.4% methane could
decompose below 850C .
The carbon due to the decomposition of methane was very active and
reacted with iron oxides immediately to reduce iron oxides to metallic iron :
2 3 21.5 2 1.5Fe O C Fe CO  

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 NO reduction by iron
2 3 22 3 1.5Fe NO Fe O N  
Since iron oxides will be reduced to iron by methane during the
reaction and then iron will reduce NO to N2 while iron will be oxidized
to iron oxides, the NO reductions will be the same whether iron or
iron oxides is used when methane is the reductant.
 2.3.3.4 NO reduction by methane over iron oxides in flue gas atmosphere
1
2
3
7
3 8
456
Experimental setup
1: gas sources; 2-flow meter; 3- ceramic tube; 4: iron/iron oxides roll; 5-
electrically heated furnace; 6- secondary oxygen input; 7- electrically
heated furnace; 8-flue gas analyzer
Simulated flue gas:1.5L/min, 0.05 vol. % NO, 2.0
vol. % O2, 17.0 vol. % CO2 in N2 base
methane: controlled by stoichiometric ratio (SR)
SR : the ratio of actual oxygen in the flue
gas and the oxygen that complete
combustion of methane requires.
SR1: redurning
SR2: burnout

2016/6/16
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300 400 500 600 700 800 900 1000 1100
0
20
40
60
80
100
NOreduction/%
temperature/
o
C
withoutFe2
O3
,SR1
=0.7,SR2
=0.7
withFe2
O3
, SR1
=0.7,SR2
=0.7
withoutFe2
O3
,SR1
=0.7,SR2
=1.2
withFe2
O3
, SR1
=0.7,SR2
=1.2
withoutFe2
O3
,SR1
=1.0,SR2
=1.0
withFe2
O3
, SR1
=1.0,SR2
=1.0
withoutFe2
O3
,SR1
=1.0,SR2
=1.2
withFe2
O3
, SR1
=1.0,SR2
=1.2
withoutFe2
O3
,SR1
=1.2,SR2
=1.2
withFe2
O3
, SR1
=1.2,SR2
=1.2
Comparison of NO reduction by methane in simulated
flue gas atmosphere when iron oxides was or was not
used (flow rate 1.5L/min, O2=2.0 vol. %, NO =0.05 vol.
%, CO2=17.0 vol. % in N2 base)
 2.3.3.4 NO reduction by methane over iron oxides in flue gas atmosphere
300 400 500 600 700 800 900 1000 1100
0
20
40
60
80
100
NOreduction/%
temperature /
o
C
SR1
=0.7, SR2
=0.7
SR1
=0.7, SR2
=1.2
SR1
=0.8, SR2
=0.8
SR1
=0.8, SR2
=1.2
SR1
=0.9, SR2
=0.9
SR1
=0.9, SR2
=1.2
SR1
=1.0, SR2
=1.0
SR1
=1.0, SR2
=1.2
SR1
=1.1, SR2
=1.1
SR1
=1.1, SR2
=1.2
SR1
=1.2
NO reduction by methane over iron oxides in
simulated flue gas atmosphere (flow rate 1.5L/min,
O2=2.0 vol. %, NO =0.05 vol. %, CO2=17.0 vol. %
in N2 base)
200 400 600 800 1000 1200
0
20
40
60
80
100
NOreduction/%
Temperature/
o
C
CH4
=0.2%
CH4
=0.4%
CH4
=0.8%
CH4
=1.0%
CH4
=1.17%, Fe2
O3
NO reduction by methane over iron
in N2 atmosphere
300 450 600 750 900 1050
0
1000
2000
3000
4000
5000
exitCO/ppm
temperature /
o
C
CH4
=0.2%
CH4
=0.4%
CH4
=0.8%
CH4
=1.0%
Exit CO when methane reducing NO over
iron in N2 atmosphere
Results showed the same results when iron/iron oxides was used.
 2.3.3.5 NO reduction by methane over iron
 NO reduction by methane over iron in N2 atmosphere

2016/6/16
27
 NO reduction by methane over iron in simulated flue gas atmosphere
300 400 500 600 700 800 900 1000 1100
0
20
40
60
80
100
NOreduction/%
temperature /
o
C
SR1
=0.7, SR2
=0.7
SR1
=0.7, SR2
=1.2
SR1
=0.8, SR2
=0.8
SR1
=0.8, SR2
=1.2
SR1
=0.9, SR2
=0.9
SR1
=0.9, SR2
=1.2
SR1
=1.0, SR2
=1.0
SR1
=1.0, SR2
=1.2
SR1
=1.1, SR2
=1.1
SR1
=1.1, SR2
=1.2
SR1
=1.2
NO reduction by methane over metallic iron in
simulated flue gas atmosphere
(flow rate 1.5L/min, O2=2.0 vol. %, NO =0.05
vol. %, CO2=17.0 vol. % in N2 base)
300 400 500 600 700 800 900 1000 1100
0
20
40
60
80
100
NOreduction/%
temperature /
o
C
without iron, SR1
=0.7, SR2
=0.7
without iron, SR1
=0.7, SR2
=1.2
with iron, SR1
=0.7, SR2
=0.7
with iron, SR1
=0.7, SR2
=1.2
without iron, SR1
=1.0, SR2
=1.0
without iron, SR1
=1.0, SR2
=1.2
with iron, SR1
=1.0, SR2
=1.0
with iron, SR1
=1.0, SR2
=1.2
without iron, SR1
=1.2, SR2
=1.2
with iron, SR1
=1.2, SR2
=1.2
Comparison of NO reduction by methane in
simulated flue gas atmosphere when iron was
or was not used(flow rate 1.5L/min, O2=2.0
vol. %, NO =0.05 vol. %, CO2=17.0 vol. % in
N2 base)
300 400 500 600 700 800 900 1000 1100
0
20
40
60
80
100
NOreduction/%
temperature /
o
C
iron, SR1
=0.7, SR2
=0.7
iron, SR1
=0.7, SR2
=1.2
iron oxides, SR1
=0.7, SR2
=0.7
iron oxides, SR1
=0.7, SR2
=1.2
iron, SR1
=1.0, SR2
=1.0
iron, SR1
=1.0, SR2
=1.2
iron oxides, SR1
=1.0, SR2
=1.0
iron oxides, SR1
=1.0, SR2
=1.2
iron, SR1
=1.2
iron oxides, SR1
=1.2
Comparison of NO reduction by methane over
metallic iron and iron oxides
(flow rate 1.5L/min, O2=2.0 vol. %, NO =0.05 vol.
%, CO2=17.0 vol. % in N2 base)
 Comparison between NO reduction by methane over iron and iron
oxides in simulated flue gas atmosphere
Yaxin Su, et al. Fuel,
2015, 160: 80-86

2016/6/16
28
 2.3.3.6 Effect of SO2 on NO reduction by iron in N2 base
200 400 600 800 1000
0
20
40
60
80
100
NOreduction/%
Tempereture/
o
C
SO2
=0.01%
SO2
=0.02%
SO2
=0.04%
Effect of SO2 on NO reduction over
metallic iron in N2 atmosphere (flow
rate 1.5L/min, NO=0.05%,
SO2=0.01%-0.04% in N2 base)
200 400 600 800 1000
0
20
40
60
80
100
SO2
reduction/%
Tempereture/
o
C
SO2
=0.01%
SO2
=0.02%
SO2
=0.04%
SO2 reduction during the
reaction of NO with iron (flow rate
1.5L/min, NO=0.05%, SO2=0.01%-
0.04% in N2 base)
10 20 30 40 50 60 70 80 90
0
100
200
300
400
500
600
700
800

 



2 /
o
Intensity(CPS)
FeO
FeS
* Fe
XRD pattern of iron sample after
reducing NO in N2 atmosphere when
SO2=0.04% (flow rate 1.5L/min,
NO=0.05%, SO2=0.04% in N2 base,
1050C)
 2.3.3.6 Effect of SO2 on NO reduction by iron in N2 base
0 10 20 30 40 50 60 70
20
40
60
80
100
NOreduction/%
durable time /hr
SO2
=0.022%
SO2
=0
Effect of SO2 on durable reduction of NO by
metallic iron in N2 atmosphere at 800 C
(flow rate 1.5L/min, NO=0.05%, SO2=0/0.022% in
N2 base, 800 C)
10 20 30 40 50 60 70 80 90
0
500
1000
1500
2000
 Fe2
O3
 Fe
+2
Fe2
+3
O4
 



















 
Intensity(CPS)
2 /
o
(a) SO2=0
10 20 30 40 50 60 70 80 90
0
1000
2000
3000
4000
5000
6000

 Fe2O3
  










Intensity(CPS)
2 /
o

(b) SO2=0.022%

2016/6/16
29
200 400 600 800 1000
0
20
40
60
80
100
NOreduction/%
Temperature /
o
C
SO2
=0.01%, CH4
=0.4%
SO2
=0.04%, CH4
=0.4%
SO2
=0.01%,CH4
=0
SO2
=0.04%, CH4
=0
Effect of SO2 on NO reduction by methane over
metallic iron in N2 atmosphere (flow rate
1.5L/min, NO=0.05%, SO2=0.01%/0.04%,
CH4=0.4% in N2 base)
 2.3.3.7 Effect of SO2 on NO reduction by methane + iron in N2 base
10 20 30 40 50 60 70 80 90
0
100
200
300
400
500
600
700
800

 



2 /
o
Intensity(CPS)
FeO
FeS
* Fe
XRD pattern of iron sample after reducing
(flow rate 1.5L/min, NO=0.05%, SO2=0.04% in
N2 base, 1050C)
10 20 30 40 50 60 70 80 90
0
100
200
300
400
500
600
700
800






Intensity(CPS)
2 /
o

 
 Fe
 Fe
+2
Fe2
+3
O4
 FeS
XRD pattern of iron sample after reducing NO by methane i
(flow rate 1.5L/min, NO=0.05%, SO2=0.04%，CH4=0.4% in
N2 base, 1050C)
300 400 500 600 700 800 900 1000 1100
0
20
40
60
80
100
NOreduction/%
Temperature /
o
C
SO2
=0, SR1
=0.7,SR2
=0.7
SO2
=0, SR1
=0.7,SR2
=1.2
SO2
=0.01%,SR1
=0.7,SR2
=0.7
SO2
=0.01%,SR1
=0.7,SR2
=1.2
SO2
=0.02%,SR1
=0.7,SR2
=0.7
SO2
=0.02%,SR1
=0.7,SR2
=1.2
SO2
=0.04%,SR1
=0.7,SR2
=0.7
SO2
=0.04%,SR1
=0.7,SR2
=1.2
Effect of SO2 on NO reduction by methane over iron
in simulated flue gas atmosphere
(flow rate 1.5L/min, O2=2.0%, CO2=16.8%,
NO=0.05%, SO2=0.01%~0.04% in N2 base)
 2.3.3.8 Effect of SO2 on NO reduction by methane + iron/iron oxides in
simulated flue gas
300 400 500 600 700 800 900 1000
0
20
40
60
80
100
NOreduction/%
Temperature /
o
C
SO2
=0, SR1
=0.7, SR2
=0.7
SO2
=0, SR1
=0.7, SR2
=1.2
SO2
=0.01%, SR1
=0.7, SR2
=0.7
SO2
=0.01%, SR1
=0.7, SR2
=1.2
SO2
=0.02%, SR1
=0.7, SR2
=0.7
SO2
=0.02%, SR1
=0.7, SR2
=1.2
SO2
=0.04%, SR1
=0.7, SR2
=0.7
SO2
=0.04%, SR1
=0.7, SR2
=1.2
Effect of SO2 on NO reduction by methane over iron
oxides in simulated flue gas atmosphere (flow rate
1.5L/min, O2=2.0%, CO2=16.8%, NO=0.05%,
SO2=0.01%~0.04% in N2 base)

2016/6/16
30
 2.3.3.9 Effect of SO2 on durable test
0 10 20 30 40 50 60 70 80 90 100
50
60
70
80
90
100
NOreduction/%
durable time / hr
Durable reaction of NO reduction by methane over iron
oxides in simulated flue gas at 1000 C (flow rate 1.5L/min,
NO=0.05%, CO2=16.8%,O2=2.0%, CH4=1.13%，
SO2=0.02% in N2 base)
20 40 60 80
0
200
400
600
800
1000
1200
1400












Fe2
O3
FeO
 Fe
+2
Fe2
+3
O
Intensity(CPS)
2 /
o

XRD pattern of iron oxides after durable
reaction with CH4 and NO at 1000 C
Yaxin Su, et al. Fuel,
2016, 170: 9-15
 2.3.3.10 Effect of water vapor
300 500 700 900 1100
0
20
40
60
80
100
H2
O=7%，SR1
=0.7，SR2
=1.2
H2
O=7%，SR1
=0.9，SR2
=1.2
H2
O=7%，SR1
=1.2，SR2
=1.2
H2
O=0%，SR1
=0.7，SR2
=1.2
H2
O=0%，SR1
=0.9，SR2
=1.2
H2
O=0%，SR1
=1.2，SR2
=1.2
NOreductionη/%
Temperature t /℃
Effect of water vapor on NO reduction with iron by
methane in simulated flue gas atmosphere (Flow rate
2L/min, NO=0.05%，O2=2.0%，H2O=7%，CO2=16.8%,
CH4 is controlled by excess air ratios)
400 600 800 1000
0
20
40
60
80
100
SR1
=0.7,SR2
=1.2,H2
O=7%,SO2
=0.02%
SR1
=0.9,SR2
=1.2,H2
O=7%,SO2
=0.02%
SR1
=1.2,SR2
=1.2,H2
O=7%,SO2
=0.02%
SR1
=0.7,SR2
=1.2,H2
O=7%,SO2
=0%
SR1
=0.9,SR2
=1.2,H2
O=7%,SO2
=0%
SR1
=1.2,SR2
=1.2,H2
O=7%,SO2
=0%
NOreductionη/%
Temperature t /℃
Effect of SO2 during the reaction of NO with iron
by methane in wet flue gas atmosphere (Flow rate
2L/min, NO=0.05%，O2=2.0%, CO2=16.8%,
H2O=7%, SO2=0.02%, CH4 is controlled by
excess air ratios in N2 base)

2016/6/16
31
 2.3.3.11 Effect of H2O+SO2 on durable test
Durable reaction of NO reduction by methane over iron oxides in simulated flue gas at 1050 C
(flow rate 2 L/min, NO = 0.05%, CO2 = 16.8%,O2 = 2.0%, CH4 = 1.14%,H2O = 7%,SO2 =
0.02% in N2 base)
0 10 20 30 40 50
50
60
70
80
90
100
NOreduction,/%
durable time / h
Zhou, Hao, Su, Yaxin*, Qi, Yuezhou, et al. J Fuel
Chem Tech ( in Chinese), 2014,42(11): 1378-1386
 2.3.3.12 C2H6 reducing NO over Fe
200 300 400 500 600 700 800 900 1000 1100
0
20
40
60
80
100
NOreduction
C2
H6
=0.1%
C2
H6
=0.2%
C2
H6
=0.3%
without iron, C2
H6
=0.1%
CH4
=0.1%, [25]
CH4
=0.2%, [25]
Temperature /
o
C
NO reduction by ethane over iron in N2 atmosphere
flow rate 2L/min, NO=0.05%, C2H6=0.1%~0.3% in N2 base
20 40 60 80
0
500
1000
1500
2000
2500
* * * *
+
+
+
+ +
+
+
+
(a) C2
H6
=0.1%
+
+ Fe3
O4
* FeO
2()
Intensity(CPS)
20 40 60 80
0
500
1000
1500
2000
2500
+
+
+ +
+
#
#
(b) C2
H6
=0.2%
+
#
2()
Intensity(CPS)
# Fe
+ Fe3
O4
XRD pattern of iron samples after reducing NO in N2 atmosphere when C2H6=0.1%/0.2%
flow rate 2 L/min, NO=0.05%, in N2 base, 1100C
COOHFeHCOFe 691035 26232 
226232 691437 COOHFeHCOFe 
20 40 60 80
0
200
400
600
800
1000
1200
(a) iron oxides before reaction
*
* *
#
#
# #
#
++
+
+
+
+
+
*#
+
Intensity(CPS)
2()
+ Fe3
O4
# Fe2
O3
* FeO
20 40 60 80
0
500
1000
1500
2000
2500
3000 ( b) after reaction with C2
H6
=0.1%
Intensity(CPS)
#
#
#
# Fe
2()
400 600 800 1000
0
20
40
60
80
100 SR1
=0.7，SR2
=1.2，C2
H6
SR1
=0.8，SR2
=1.2，C2
H6
SR1
=0.9，SR2
=1.2，C2
H6
SR1
=1.0，SR2
=1.2，C2
H6
SR1
=1.1，SR2
=1.2，C2
H6
SR1
=1.2，SR2
=1.2，C2
H6
SR1
=0.7，SR2
=1.2，CH4
SR1
=0.8，SR2
=1.2，CH4
SR1
=0.9，SR2
=1.2，CH4
SR1
=1.0，SR2
=1.2，CH4
SR1
=1.1，SR2
=1.2，CH4
SR1
=1.2，SR2
=1.2，CH4
NOreduction/%
Temperature /
o
C
Comparison of NO reduction by ethane and methane over iron in simulated
flue gas atmosphere flow rate 2L/min, O2=2.0%, CO2=17.0%, NO=0.05%, in
N2 base
DOU Yifeng, SU Yaxin*, et al. J Fuel
Chem Tech ( in Chinese), 2015,
43(10):1273-1280

2016/6/16
32
200 300 400 500 600 700 800 900 1000 1100
0
20
40
60
80
100
NOreduction
Temperature /
o
C
C3
H8
=0.05%
C3
H8
=0.1%
C3
H8
=0.2%
CH4
=0.2%
CH4
=0.4%
NO reduction by propane over iron in N2 atmosphere
（flow rate 2L/min, NO=0.05%,C3H8=0.05%-0.2% in
N2 base）
20 40 60 80 100
0
500
1000
1500
2000 (a) C3
H8
=0.1%，XRD
+
+
**** ***
* Fe3
O4
+ Fe
Intensity(CPS)
/
o
*
+
20 40 60 80 100
0
500
1000
1500
2000
2500
3000
(b) C3
H8
=0.2%，XRD
/
o
*
*
*
* Fe
Intensity(CPS)
C3H8=0.1%,SEM
C3H8=0.2%,SEM
300 400 500 600 700 800 900 1000
0
20
40
60
80
100
?
NOreduction/%
Temperature /
o
C
SR1
=0.7, SR2
=1.2, C3
H8
SR1
=0.8, SR2
=1.2, C3
H8
SR1
=0.9, SR2
=1.2, C3
H8
SR1
=1.0, SR2
=1.2, C3
H8
SR1
=1.1, SR2
=1.2, C3
H8
SR1
=1.2, SR2
=1.2, C3
H8
SR1
=0.7, SR2
=1.2, CH4
SR1
=0.8, SR2
=1.2, CH4
SR1
=0.9, SR2
=1.2, CH4
SR1
=1.0, SR2
=1.2, CH4
SR1
=1.1, SR2
=1.2, CH4
SR1
=1.2, SR2
=1.2, CH4
Comparison of NO reduction by propane and methane over metallic iron in simulated
flue gas atmosphere (flow rate 2L/min, O2=2.0%, NO=0.05%, CO2=17.0%, in N2
base)
SU, Yaxin, et al. J Fuel Chem Tech ( in
Chinese), 2014, 42(12): 1470-1477
400 600 800 1000 1200
0
20
40
60
80
100 SR1
=SR2
=0.7
SR1
=0.7, SR2
=1.2
SR1
=SR2
=0.8
SR1
=0.8, SR2
=1.2
SR1
=SR2
=0.9
SR1
=0.9, SR2
=1.2
SR1
=SR2
=1.0
SR1
=1.0, SR2
=1.2
SR1
=SR2
=1.1
SR1
=1.1, SR2
=1.2
SR1
=SR2
=1.2
NOreduction
Temperature /
o
C
C3H6 reducing NO over Fe (flow rate 2L/min,
O2=2.0%, NO=0.05%, CO2=17.0%, in N2 base)
4 00 600 8 00 10 00 120 0
0
20
40
60
80
1 00
NOreduction/%
Temperature /
o
C
H 2
O =7% ,SO 2
=0.02% , SR1
=0.7, SR2
=1.2 H2
O =7% ,SO 2
=0,SR1
=0.7, SR 2
=1.2
H 2
O =7% ,SO 2=0.02% ,SR1
=0.9, SR2
=1.2 H2
O =7% ,SO 2
=0,SR1
=0.9, SR2
=1.2
H 2
O =7% ,SO 2
=0.02% ,SR1
=1.0, SR2
=1.2 H2
O =7% ,SO 2
=0,SR1
=1.0, SR 2
=1.2
H 2
O =7% ,SO 2
=0.02% ,SR1
=SR2
=1.2 H2
O =7% ,SO 2
=0,SR1
=SR2
=1.2
Effect of SO2 and H2O on C3H6 reducing NO over Fe
(flow rate 2L/min, O2=2.0%, NO=0.05%, CO2=17.0%,
H2O=0-7%, SO2=0-0.02%, in N2 base)
LIANG Jun-qing, SU Ya-xin*, et al. J Fuel Chem
Tech ( in Chinese), 2016 （in press)

2016/6/16
33
Major shortcomings
 The reaction happens above 850 C may be a major
shortcoming for the application of NO reduction by
hydrocarbons. So, it is necessary to try to find a catalyst
based on iron which is effective at lower temperature.
 Iron-supported catalysts were tested.
2.4 iron based supported catalyst for SCR-HC
 2.4.1 Monolithic cordierite-based Fe/Al2O3 catalysts
10 20 30 40 50 60 70 80
SO2-treated catalyst
H2O-treated catalyst
Fresh catalyst
○ 2MgO·2Al2O3·5SiO2
● Fe2O3
Intensity/(CPS)
2θ /(°)
○
○
○
○
○ ○
○
○
○ ○ ○
○
●●
●
●
● ●
Fe3+ supported on ceramic honeycomb cordierite by sol/gel- impregnation
method and calcined at 500C for 5 h with Fe load 6 wt% (fresh catalyst), The
fresh catalysts were exposed to gas stream containing either 10% H2O or
0.02% SO2 at a flow rate of 1500 ml/min at 700C for 24 h and were noted as
“H2O-treated” or “SO2-treated” catalyst.
Fe/Al2O3/cordierite

2016/6/16
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 2.4.2 NO reduction with C3H8
(a) 500 ppm NO, 800 ppm C3H8, GHSV =18000 h-1
200 300 400 500 600
0
20
40
60
80
100
NOx
C3H8
Temperature (°C)
NOxConversion(%)
0
20
40
60
80
C3H8Conversion(%)
(a)
200 300 400 500 600 700
0
20
40
60
80
100
NOx
C3H8
Temperature (°C)
NOxConversion(%)
0
20
40
60
80
100
C3H8Conversion(%)
(b)
(b) 500 ppm NO, 0.3% C3H8, 1% O2, GHSV
=18000 h-1
200 300 400 500 600 700
0
20
40
60
80
100
NOxConversion(%)
Temperature (°C)
Fresh catalyst
H2O-treated catalyst
SO2-treated catalyst
 2.4.3 Effect of H2O/SO2
0 2 4 6 8 10 12
0
20
40
60
80
100
550°C
Removing SO
2
Reaction tiome t/h
Adding H
2
O
NOxConversion(%)
Adding SO
2
Removing H
2
O
600°C
500 ppm NO, 0.3% C3H8, 1% O2, 0.02% SO2 (when used), 2.5% H2O (when used),
GHSV =18000 h-1, T = 600 /550℃

2016/6/16
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 2.4.3 DRIFT in situ study-H2O
In situ DRIFTS of NO and C3H8 adsorption over the Fe/Al2O3/
cordierite catalyst at 200 C in the presence of 2.5% H2O.
NO2
adspecies
bidentate
nitrate unidentate
acetate
formate
When 2.5%H2O was introduced, NO2 adspecies
disappeared, bidentate nitrate (1596 cm−1) showed
red shift to 1570 cm−1，unidentate (1299cm-1)
became weak-H2O disturbed the adsorption
60 min after introducing 2.5%H2O , acetate (1471
cm-1) and formate (1376 cm-1) had no change--the
inhibition effect of H2O on acetate/formate species
was negligible
When H2O was cut-off, everything
almost recovered, which indicated
that H2O had a reversible
influence on the adsorption on
catalyst surface
In situ DRIFTS of NO and C3H8 adsorption over the
Fe/Al2O3/cordierite catalyst in the presence of
0.2% SO2.(200℃)
When 0.2% SO2 was introduced, surface nitrate species at
1299,1596, 1628 cm-1 decrease in intensity,
unidentate nitrate band (1299 cm-1) completely
disappeared after 30 min, sulphate species (1328 cm-1)
appeared due to the deposited SO4
2- species
acetate species (1471 cm-1) and formate species (1376
cm-1) increased gradually with time in the presence of
SO2.
When SO2 was shut-off, nitrate and acetate/formate
species recovered slightly
adsorbed sulphate species still exist，which indicated
that SO2 had an irreversible influence on the adsorption
on catalyst surface
 2.4.4 DRIFT in situ study-SO2

2016/6/16
36
2.4.5 Mechanism
Hao Zhou, Yaxin Su*, Wenyu Liao, et al. Fuel,
2016, 182：352-360
Coexisting H2O influenced the formation NO2 adspecies and unidentate nitrate, while SO2
slightly inhibited the formation of NO2/NO3
− species, but promoted the formation of
acetate/formate species during NO reduction by C3H8.
 2.4.6 Monolithic cordierite-based Fe/Al2O3 catalysts for NO reduction with C2H6
SEM of Fe/Al2O3/cordierite
（a）CM after acid solution
treatment
（b）Al2O3/CM
（c）5.5Fe/Al2O3/CM （d）8Fe/Al2O3/CM
200 300 400 500 600
0
20
40
60
80
100
2Fe/Al2
O3
/CM
3.5Fe/Al2
O3
/CM
5.5Fe/Al2
O3
/CM
8Fe/Al2
O3
/CM
5Fe/CM
Al2
O3
/CM
Fe2
O3
NOxConversion(%)
Temperature (℃)
(a)
200 300 400 500 600
0
10
20
30
40
50
60
70
80
2Fe/Al2
O3
/CM
3.5Fe/Al2
O3
/CM
5.5Fe/Al2
O3
/CM
8Fe/Al2
O3
/CM
5Fe/CM
Al2
O3
/CM
Fe2
O3
C2H6Conversion(%)
Temperature (℃)
(b)
NOx conversion to N2 (a), C2H6 conversion (b) over Fe/Al2O3/cordierite (500 ppm NO, 1000 ppm C2H6, and GHSV=18000 h-1)
4000 3500 3000 2500 2000 1500 1000
1303
1570
1240
1322
1420
2220
1903
1842
1602
1628
RT in NO
400°C
350°C
300°C
250°C
200°C
150°C
100°C
50°C
Absorbance(a.u.)
Wavenumber (cm
-1
)
RT in NO and C2
H6
3730
3770
0.1
Infrared spectra in the absence of O2 after the
5.5Fe/Al2O3/CM catalyst was exposed to 2% NO for 30 min
followed by introduction of 2% C2H6 at room temperature.
10 20 30 40 50 60 70 80
●
●
●
●
○
3.5Fe/Al2O3/CM
5.5Fe/Al2O3/CM
○2Al2O3·2MgO·5SiO2 ●Fe2O3
8Fe/Al2O3/CM
2Fe/Al2O3/CM
Al2O3/CM
Cordierite
○
○○○○
○
○○○○
○
○
● ●
Intensity(CPS)
2θ (°)
XRD pattern
Hao Zhou, Yaxin Su*, Wenyu
Liao, et al. Applied Catalysis A:
General, 2015, 505: 402- 409

2016/6/16
37
2.5 Quantum chemistry calculation of NO +Fe2
 B3LYP/6-311+G(d, p) basis set
 Gaussian 09

2016/6/16
38
Erel/（kCal ∙ mol-1） E'/( kCal ∙ mol-1)
octet decuplet octet decuplet
Fe2+NO 0 4.21 - -
C1(C1') -48.25 -25.20 - -
TS1(TS1') -26.88 -16.97 21.37 8.23
C2(C2') -50.86 -32.63 - -
TS2(TS2') -40.76 -28.26 10.10 4.37
C3(C3') -64.84 -61.88 - -
TS3(TS3') -54.19 -39.72 10.65 22.16
C4(C4') -54.58 -39.86 - -
TS4(TS4') -5.05 -9.25 49.53 30.61
Fe2O+N -71.47 -102.24 - -
benchmark
Reaction activation
energy results from
the cleavage of N-
O bond.
Energies of various species in reaction of Fe2+NO→Fe2O+N on two state
PES
2.6 Microwave-Induced Sewage Sludge Pyrolysis
 2.6.1 Microwave heating introduction
Single-mode microwave heating device
Microwave heating principle
Main Advantages of microwave heating
 Precisely controllable and can be turned on and off instantly
 More compact, requiring a smaller equipment footprint
 Non-contact heating technology
 Microwave energy provides uniform energy distribution

2016/6/16
39
0
50
100
150
200
250
300
350
400
450
0
100
200
300
400
500
600
700
800
900
0 5 10 15 20 25
Temperature
Gas product
Temperautre/⁰C
Gasproductflowrate/mlmin-1
t/min
(b)
温度
气相产物
温度
气相产率/(ml/min)
Gas production evolution during microwave pyrolysis
Temperature
Gasproduction
0
5
10
15
20
25
30
35
40
45
50
55
60
65
CO2CH4COH2
ZnCl2: DS=1:2
(wt/wt)
水蒸气流量
1.59g/min
Gasconcentration/vol.%
400-700℃
700-850℃
>850℃
CaO: DS=1:2
(wt/wt)
水蒸气流量
1.59g/min
H2 CO CH4 CO2
体积分数/vol.%
800~950℃
700~800℃
400~700℃
Pyrolysis gas distribution under combined
effect of catalyst and steam
Volumefraction
Steam flow Steam flow
 2.6.2 Sewage sludge pyrolysis for hydrogen production
0
5
10
15
20
25
30
35
40
45
50
55
60
65
Gasconcentration/vol.%
DS
CaO: DS=1:2(wt/wt)
ZnCl2: DS=1:2(wt/wt)
水蒸气流量 1.59g/min
CaO: DS=1:2(wt/wt),水蒸气
流量1.59g/min
ZnCl2: DS=1:2(wt/wt),水蒸气
流量1.59g/min
H2 CO CH4 CO2
体积分数/vol.%
CaO:DS = 1:2
ZnCl2:DS = 1:2
CaO:DS = 1:2, 水蒸气流量
1.59 g/min
ZnCl2:DS = 1:2, 水蒸气流量
1.59 g/min
水蒸气流量1.59 g/min
Comparison of gaseous distributions under different microwave pyrolysis
conditions (850 ºC)
Volumefraction
Steam flow
Steam flow
Steam flow
 2.6.3 Methane decomposition over sludge residue for hydrogen production
0
100
200
300
400
500
600
700
800
900
1000
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 20 40 60 80 100 120
320 W, 0.3 L g-1 h-1
320 W, 0.15 L g-1 h-1
320 W,0.3 L g-1 h-1
320 W, 0.15 L g-1 h-1
A
B
a
b
100
80
60
40
20
0
Time (min)
Temperature(ºC)
CH4conversion(%)
Temperature and methane conversion over pyrolysis residue under microwave
heating. A and a: 320 W, 0.3 L g-1 h-1; B and b: 320 W, 0.15 L g-1 h-1.
0
1000
2000
3000
4000
5000
6000
0 10 20 30 40 50 60 70 80 90
2θ(º)
Counts
(a)
(b)
Quartz– SiO2
Anorthite– CaAl2(SiO2)4
Kaolinite– Al2SiO5
XRD ananlysis of the molten beads
Molten beads (left) and nano-tubes formed over pyrolysis residue
by microwave induced methane decomposition.
Wenyi Deng, Yaxin Su, Shugang Liu, et al. International
Journal of Hydrogen Energy. 2014, 39: 9169-9179.

2016/6/16
40
3. Professors outside China visit my lab
3.1 Prof Wei-Yin Chen, the University of Mississippi, USA, 2003, 2005, 2009
3.2 Prof Miguel Castro, Universidad Nacional Autónoma de México (UNAM), 2015.10

2016/6/16
41
3.3 Prof Saffa Riffat，the University of Nottingham, UK, 2004, 2015;
4. My group

2016/6/16
42
4. My group
Thank you and
welcome to visit
Shanghai!

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