Professor Jianrong QiuProfessor Jianrong Qiu

State Key Laboratory of Coal CombustionState Key Laboratory of Coal CombustionHuazhong University of Science and TechnologyHuazhong University of Science and Technology

Wuhan, Hubei 430074, P.R.ChinaWuhan, Hubei 430074, P.R.China

CO2 Capture and SequestrationResearch in SKLCC

COCO22 Capture and Capture and SequestrationSequestrationResearch in Research in SKLCCSKLCC

International Workshop on Clean Coal Technology Development--CO2 Mitigation, Capture, Utilization and Sequestration

August, 2005, Beijing, China

Introduction of SKLCCIntroduction of SKLCC

Current Research and Progress Current Research and Progress

Ongoing and Future WorkOngoing and Future Work

OutlineOutlineOutline

History: 1981Faculty and Staffs: 30 Graduate Students: 150

History: 1981History: 1981Faculty and Staffs: 30 Faculty and Staffs: 30 Graduate Students: 150Graduate Students: 150

Coal Combustion Science Coal Combustion Science

Combustion Pollution and Control

Combustion Pollution and Control

•SO2

•NOx,N2O•Trace Elements•PAHs• CO2 Capture

•SO2

•NOx,N2O•Trace Elements•PAHs• CO2 Capture

Combustion Model and Simulation

Combustion Model and Simulation

Combustion Diagnosis and Application of

Computer

Combustion Diagnosis and Application of

Computer

Combustion TechnologyCombustion Technology

Advanced Power Generation Technology

Advanced Power Generation Technology

Res

earc

h A

reas

Res

earc

h A

reas

Res

earc

h A

reas

Thermal Physical and Chemical Properties

Thermal Physical and Chemical Properties

Coal Structure and Reactivity

Coal Structure and Reactivity

•Aerodynamic Model

•Heat Transfer

•Combustion Model

•Pollution Model

•Global Simulation of Combustion Process

•Aerodynamic Model

•Heat Transfer

•Combustion Model

•Pollution Model

•Global Simulation of Combustion Process

Computer Management Monitor and Control System

Computer Management Monitor and Control System

Combustion DiagnosisCombustion Diagnosis

Pulverized Coal Combustion

Pulverized Coal Combustion

Fluidized Bed Combustion

Fluidized Bed Combustion

Gasification and Flue Gas Cleaning

Gasification and Flue Gas Cleaning

O2/CO2 CombustionO2/CO2 Combustion

International publications: more than 200International publications: more than 200International publications: more than 200

(1997-2004)

MIT (US)MIT (US)

University of Connecticut (US)University of Connecticut (US)

University of Utah (US)University of Utah (US)

West Kentucky University (US)West Kentucky University (US)

University of Albert (Canada)University of Albert (Canada)

Clumbia University (Canada)Clumbia University (Canada)

Inte

rnat

iona

l C

oope

ratio

nIn

tern

atio

nal

Inte

rnat

iona

l C

oope

ratio

nC

oope

ratio

n

University of Newcastle (Australia) University of Newcastle (Australia)

Current Research and Progress in SKLCC

Current Research and Progress in Current Research and Progress in SKLCCSKLCC

Oxy-fuel Combustion

Chemical LoopingChemical Looping CombustionCombustion

CO2 Capture Based on CCR

COCO22 Sequestration by Mineral Sequestration by Mineral

CarbonationCarbonationNSFC(1997-) (2001-)(2002-) ; 973 Program(1999-2004); 985 Program (2005-)

Oxy-Fuel CombustionOxyOxy--Fuel CombustionFuel Combustion

CO2 concentration: 95%

NOx reduction: 30%-70%

SO2 removal by limestone: 40%-90%

Thermal efficiency increase: 3%Easy and efficient CO2separation, recovery

Highly efficient, clean coal combustion

・Low SO2 emission

O2/CO2 Pulverized coal combustion・Easy and efficient CO2 separation・Extremely low NOx emission

Characteristics and mechanisms

unknown

Recycled gas

Coal

O2

How about NOx and SOx emissionsin O2/CO2 pulverized coal combustion?

Recirculation of mass

Enrichment of mass(CO2，NOx，SOx) in furnace

Small amount of exhaust gas

Furnace

Small amount of exhausted gasas a system

CaSO4 decomposition

Low desulfurization efficiency

Conventional pulverized coal combustion

Recycled-S

High CO2 concentration

・Enhance desulfurizationreaction?・Inhibit CaSO4 decomposition?

Possibility of high in-furnacedesulfurization efficiency

O2/CO2 pulverized coal combustion

Fuel-S (SO2)

Fuel-S (SO2)

Coal

Coal

Characteristics and mechanisms: unknown

SKLCC’s ProgressSKLCCSKLCC’’s Progresss Progress

Flame Characteristics and Combustion behavior

The mechanism of SO2 and NOx reduction

Limestone desulfurization reaction mechanism in O2/CO2

O2/N2 或O2/CO2

O2/N2 或O2/CO2

试样

1 2 3

4567

1 硅炭管 2 石英管 3 热电偶 4 计算机 5 温控仪 6 烟气分析仪 7 保温带

Experimental FacilityExperimental FacilityExperimental Facility

TGA-FTIRTGATGA--FTIRFTIR

N2

O2

CH4

NO CO2

Ar

1 2

43

5

6 7

8

1 点火器2 混气器3 热电偶4 反应器5 取样管6 过滤器7 干燥器8 烟气分析仪

CH4 combustion deviceCH4 combustion deviceCH4 combustion device

O2/CO2 Coal Combustion FurnaceO2/CO2 Coal Combustion Furnace

1O2/CO2或O2/N2

2

34

5 6

7

8

910

11

0 1 2 3 4 5 6 7 8700

750

800

850

900

950

1000

T/¡æ

d/cm

¦Ë=1.0 ¦Ë=1.1

0 1 2 3 4 5 6 7 8700

750

800

850

900

950

1000

d/cm

T/¡æ

¦Ë=0.8 ¦Ë=1.0 ¦Ë=1.1

60%CO2 40%CO2

Flame CharacteristicsFlame CharacteristicsFlame Characteristics

SO2 EmissionSOSO2 2 EmissionEmission

0 200 400 600 800 1000

0

50000

100000

150000

200000

250000

300000

350000

400000

450000

hs1a hs3a hs1b hs3b hs5b

SO2 c

once

ntra

tion

inte

grat

ion

Vso

2/Vflu

e ga

s*10-6

.seco

nd

t (s) Abs

orba

nce

0.00

0.07

0.14

1300 1400 1500

spectrum number Cm-1

80% CO2

40% CO2

15% CO2

air

a: air, b: O2/CO21: 700℃, 3: 900℃ 5: 1000℃

2

2 2

2 2 2

22

32 22

C CO COCO SO CO S

CO S COS

SO COS CO S

+ →+ → ++ →

+ → +

air

O2/CO2

SO2 emission decreased about 30-60% for different coals at different temperatures

0

10

20

30

40

50

60

70

80

90

1 2 3 4 5

Air

O2/CO2

SO2 Removal by LimestoneSOSO22 Removal by LimestoneRemoval by Limestone

Ca/S mol ratio

Des

ulfu

riza

tion

effic

ienc

y %

1000 1100 1200 1300 1400 1500 1600 1700

02468

101214161820222426

rate

of d

ecom

posit

ion

%

T/K

CO2=0 CO2=0.4 CO2=0.7

The presence of high concentration COThe presence of high concentration CO22 can improve the can improve the SOSO22 removal efficiency with limestone injection. removal efficiency with limestone injection.

CaSO4 decomposition

Low CO2 concentration High CO2 concentration

Indirect sulfation:

CaCO3 = CaO + CO2

CaO + (1/2)O2 + SO2 = CaSO4

Direct sulfation:

CaCO3 + (1/2)O2 + SO2 = CaSO4 + CO2

CaCO3 does not decomposeCaCO3decomposes

CaO SinteringSO2 is difficult to get into the particleLow reaction rate

Sintering is mitigatedCO2 formation and diffusion results in aporous product layer SO2 is easy to get into the particle

CaSO4

CaCO3

CO2

SO2/O2

Pore

SO 2

CaSO4

SO2/O2

CaO

Fundamental MechanismsFundamental MechanismsFundamental Mechanisms

SO2 reduction mechanism in Oxy-fuel recycle combustion system

SOSO22 reduction mechanism in Oxyreduction mechanism in Oxy--fuel recycle combustion systemfuel recycle combustion system

About four times longer than in conventional coal combustion owing to gas recirculation

Increase of η due to inhibition of CaSO4 decomposition

Increase of η due to recirculation of flue gas (sorbents)

Higher Limestone desulfurization efficiency

Small amount of exhausted gas

Small amount of SO2 emission

COS formation

SO2 retention by CaO in the coal

NOx EmissionNOxNOx EmissionEmission

700 800 900 1000 110050

100150200250300350400450

NO

x(pp

m)

T(0C)

hsa hsb spsa spsb dpqa dpqb

a:a: Air, Air, b:b: OO22/CO/CO22

C+CO2→2CO

NO＋CO→CO2＋1/2 N2

C+2NO→CO2+N22C+2NO→2CO+N2

煤中矿物质尤其是Fe和Ca的存在对半焦与NO的反应有催化作用.

air

O2/CO2

NOx emission decreased about 10-40% for different coals at different temperatures

NOx Emission in DesulfurizationNOxNOx Emission in Emission in DesulfurizationDesulfurization

700 750 800 850 900 950 1000

100

150

200

250

300

350

400

NO

x pp

m

T/℃

HS-O2/N

2 HS-O2/CO2 SPS-O2/N2 SPS-O2/CO2 DPQ-O2/N2 DPQ-O2/CO2

CaCO3的存在对CO与NO的表面反应有催化作用.

air

O2/CO2

NO reduction mechanism in Oxy-fuel recycle combustion system

NO reduction mechanism in OxyNO reduction mechanism in Oxy--fuel recycle combustion systemfuel recycle combustion system

Decrease of N conversion due to increase of CO2concentration

Small amount of NO emission

Interaction between fuel-N and recycled NO

Reduction of recycled NO in the furnace

Small amount of exhausted gas

No thermal NO

0.00E+00

2.00E-05

4.00E-05

6.00E-05

8.00E-05

1.00E-04

1.20E-04

1.40E-04

1.60E-04

1.80E-04

1000 1100 1200 1300 1400 1500 1600 1700 1800

温度

Na蒸

发量

mol

O2/CO2

空气

0.00E+00

1.00E-03

2.00E-03

3.00E-03

4.00E-03

5.00E-03

6.00E-03

7.00E-03

8.00E-03

1000 1100 1200 1300 1400 1500 1600 1700 1800

温度

Fe蒸

发量

mol

O2/CO2

空气

0.00E+00

5.00E-03

1.00E-02

1.50E-02

2.00E-02

2.50E-02

3.00E-02

1000 1100 1200 1300 1400 1500 1600 1700 1800

温度

K蒸

发量

mol

O2/CO2

空气

Mineral TransformationMineral TransformationMineral Transformation

Current Research and Progress in SKLCC

Current Research and Progress in Current Research and Progress in SKLCCSKLCC

Oxy-fuel Combustion

Chemical LoopingChemical Looping CombustionCombustion

CO2 Capture Based on CCR

COCO22 Sequestration by Mineral Sequestration by Mineral

CarbonationCarbonationNSFC(1997-) (2001-)(2002-) ; 973 Program(1999-2004); 985 Program (2005-)

or H2, CO, Coal

oxidation reactor

Reduction Reactor

Chemical Looping CombustionChemical Looping CombustionChemical Looping Combustion

金属氧化物作为氧载体

在大规模应用中必须考虑的

一个问题是金属氧化物会进

入大气环境，为新的污染

源。因此，探索新的非金属

氧载体物质也是一项非常重

要的工作。

New Oxygen Carrier is New Oxygen Carrier is developed instead of metal developed instead of metal Oxygen Carrier (Oxygen Carrier (NiONiO/Ni/Ni，，FeFe22OO33/Fe/Fe33OO44, , CoOCoO/Co, /Co, CuOCuO/Cu/Cu，，MnMn33OO44/MnO etc.)/MnO etc.)

CH4(CO,H2) + N-MeOx → CO2 + H2O + N-Me

N-Me + 2O2 → NMeOx

New Oxygen CarrierNew Oxygen CarrierNew Oxygen Carrier

A Novel non-metal oxides: no secondary pollution A Novel nonA Novel non--metal oxides: no secondary pollution metal oxides: no secondary pollution

0 200 400 600 800 1000 120040

50

60

70

80

90

100

110

质量

/ %

温度 / oC

TG

-16

-14

-12

-10

-8

-6

-4

-2

0

2DTG

DTG

TG--FTIR experiment for reaction system of non-metal oxides with CH4

Current Research and Progress in SKLCC

Current Research and Progress in Current Research and Progress in SKLCCSKLCC

Oxy-fuel Combustion

Chemical LoopingChemical Looping CombustionCombustion

CO2 Capture Based on CCR

COCO22 Sequestration by Mineral Sequestration by Mineral

CarbonationCarbonationNSFC(1997-) (2001-)(2002-) ; 973 Program(1999-2004); 985 Program (2005-)

CO2 Capture Technology Based on Carbonation/Calcination ReactionsCOCO22 Capture Technology Based on Capture Technology Based on Carbonation/Carbonation/CalcinationCalcination ReactionsReactions

I — CO2 Capture During Combustion

Capture: CaO + CO2 → CaCO3

Regeneration：CaCO3 → CaO + CO2

Separation Energy:CCR process 84 kWh/ton CO2

MEA process 203 kWh/ton CO2

II — CO2 Capture During Gasification

CO2 Capture Technology Based on Carbonation/Calcination ReactionsCOCO22 Capture Technology Based on Capture Technology Based on Carbonation/Carbonation/CalcinationCalcination ReactionsReactions

1) Syngas CO/H2

Water Gas Shift Reaction:

CO + H2O → CO2 + H2

CaO + CO2 → CaCO3

CaCO3 → CaO + CO2

2) CH4 + 2H2O + CaO →

CaCO3 +4H2

CaCO3 → CaO + CO2

☆ CO2 Capture： CaO + CO2 → CaCO3

☆ Regeneration： CaCO3 → CaO + CO2

– Experimental Research• Calcination Kinetics at CO2 and N2 atmosphere • Carbonation Reaction

– Numerical Simulation• Calcination model for dispersed limestone particle(弥散石灰石煅烧模型)

• Fractal model for dispersed limestone decomposion (石灰石分解的分

数维模型

• Freedom pore model for carbonation of CaO under high pressure (高压下的随机孔模型)

Two-Core ReactionsTwoTwo--Core ReactionsCore Reactions

Calcination Kinetics at CO2 and N2 AtmosphereCalcinationCalcination Kinetics at COKinetics at CO22 and Nand N22 AtmosphereAtmosphere

940 960 980

0.0

0.2

0.4

0.6

0.8

1.0

转化

率

T ( oC )

3 oC/min 5 oC/min 7 oC/min 10 oC/min 15 oC/min

850 900 950 1000 1050 1100

0.0

0.2

0.4

0.6

0.8

1.0

α

T / K

5 K/min 7 K/min 10 K/min 20 K/min 30 K/min

CO2 N2

n=2/3，mechanistic function ，

CO2 atmosphere，Eα→0=975.38kJ/mol; N2atmosphere，Eα→0=243.62kJ/mol

Carbonation Characteristic of CaOCarbonation Characteristic of Carbonation Characteristic of CaOCaO

CaO conversion ratio vs. CO2 concentration CaO conversion ratio vs. temperature

Current Research and Progress in SKLCC

Current Research and Progress in Current Research and Progress in SKLCCSKLCC

Oxy-fuel Combustion

Chemical LoopingChemical Looping CombustionCombustion

CO2 Capture Based on CCR

COCO22 Sequestration by Mineral Sequestration by Mineral

CarbonationCarbonation

NSFC(1997-) (2001-)(2002-) ; 973 Program(1999-2004); 985 Program (2005-)

该技术原理是基于CO2与矿物在一定条件下反应生成稳定、无污染的碳酸盐，以实现二氧化碳的储存。例如CO2与硅酸盐矿物反应生成碳酸盐，二氧化硅和水并且放出热量。

CO2 Sequestration by Mineral CarbonationCOCO2 2 Sequestration by Sequestration by Mineral CarbonationMineral Carbonation

The family of reactions:(Mg, Ca)xSiyOx+（2y+z）H2 （z+x）CO2 → x(Mg,Ca)CO3 + ySiO2 +zH2O

Serpentine:• MgO38-45%(wt%）• Fe2O35-8 %(wt%）• H2O13 %(wt%）• Reaction releases heat ：+ 64 kJ/mole• One ton of serpentine can dispose of

approximately one-half ton of CO2

Olivine：• MgO45-50%(wt%）• Fe2O3 6-10%(wt%）• Reaction releases heat：+ 95 kJ/mole• One ton of olivine can dispose of

approximately two-thirds of a ton of CO2

CO2 Mineral CarbonationCOCO22 Mineral CarbonationMineral Carbonation

Experimental FacilityExperimental FacilityExperimental Facility

※ 问题： 1）碳酸化速率太慢； 2）能耗高，隔离成本大。

※ 解决途径： 减小颗粒粒径、添加催化溶液、表面预处理。

X-ray diffraction pattern for serpentine HT 650 feed ample and reaction

XRD AnalysisXRD AnalysisXRD Analysisantigorite (An)forsterite (Fo).

Magnesite (Ms)Antigorite（An）

• Sample was from an experiment in which the serpentine (heat treated at 650℃ for • 2 hrs) was exposed in a stirred autoclave to an aqueous solution of sodium • bicarbonate and sodium chloride for one-half hour at T=155℃ and Pco2=100 atm.

rhombohedralmagnesite

crystals(菱铁矿)serpentine(蛇

纹石)

• . Serpentine HT-650 reaction productsSerpentine HT-650 reaction products

Introduction of SKLCCIntroduction of SKLCC

Current Research and Progress in Current Research and Progress in

SKLCCSKLCC

Ongoing and Future WorkOngoing and Future Work

OutlineOutlineOutline

Ongoing and future worksOngoing and future worksOngoing and future works

Oxy-fuel recycle combustion

Chemical Looping Combustion fueled by coal

Explore other CO2 capture and SequestrationSequestrationmethod

Grant: 985 Program---Clean Combustion & Thermal Energy ConversionFunding: RMB 12 Million

Oxy-fuel recycle combustion systemOxyOxy--fuel recycle combustion systemfuel recycle combustion system• Pilot-Scale flow chart (under construction)

300KW, inner diameter 600mm，height 8m.

Detect CO2 concentration . (recycle ratio)Combustion behavior for typical Chinese coals (is feasible for retrofit application?)SO2/NOx emission and Control, ash deposition

Future work

Chemical Looping Combustion fueled by coal(以煤直接为燃料的化学链

燃烧系统)

a riser type oxidizer rector, a bubbling, two-compartment, pressurized fluidized reduction reactor

Thank You!