Coal combustion in

oxygen-enriched atmosphere in
regenerator of CaL process

T. Shimizu, C. Gao, T. Takahashi,

H. Narisawa, S. Furukawa, A. Yoshizawa,
H.-J. Kim, L. Li
Niigata University, Japan

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 CaL process
CaL process consists of an absorber and a
regenerator. In the regenerator, coal is burned to
supply heat for CaCO3 decomposition.
CO 2 -free gas CO 2 , H 2 O

CaO
Absorber Regenerator
(873 K) (1223 K)
Heat CaCO 3
removal

Flue gas Fuel O 2 CO 2 for

(Coal) dilution
2
 Anticipated problems with regenerator
Coal combustion at high temp. & in high O2 conc.
 NOx formation  HNO3 during compression
CO 2 -free gas CO 2 , H 2 O , NOx H 2O

CaO HNO3
Fuel- N
CaCO 3 NOx

Flue gas Fuel O 2 CO 2

Absorber Regenerator
3
 Anticipated problems with regenerator
Coal combustion  Char formation in regenerator
 Char transportation to absorber  CO and CO2
CO 2 -free gas CO 2 , H 2 O
CO, CO2
Char
CaO
Char
particles
CaCO 3
in Reg.

Flue gas Fuel O 2 CO 2

(Low O2 conc.)
Absorber Regenerator
4
 Objectives of this work
A bench-scale fluidized bed solid circulation
system was operated using inert sand bed. Coal
combustion experiments were conducted using
oxygen-enriched air to evaluate
NOx formation in regenerator,
formation of CO and CO2 in absorber, and
effect of fuel type on emissions.

5
 Objectives of this work (continued)
Carbon capture by porous material (porous CaO),
is proposed as an approach to stabilize volatile
matter combustion in regenerator.

6
 Experimental
(1) Coal combustion experiments using a bench-
scale solid fluidized bed circulation system
(Detail will be published soon in “E.J. Anthony honor issue” of FUEL.)

(2) Volatile matter capture by calcined limestone

at elevated temperatures using a fixed bed
reactor

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Reg. flue Twin-fluidized bed solid circulation system
gas
Regenerator: Fast bed
ID 2.2 cm, height 1.93 m
Abs. flue
gas
Gas vel. 2.7 m/s at 950 oC
O2-enriched air feed (30% O2)
Fuel feed

O 2 /Air (Sec.)
Air Absorber: Bubbling bed
Fuel ID 9.3 cm, bed height 0.3 m
Gas vel. 0.22 m/s at 600 oC

Air
Air feed
O 2 /Air (Prim.)
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 Experimental (1) : Coal combustion in twin-
fluidized bed solid circulation system
Fuel type:
High-volatile bituminous coal
Medium-volatile bituminous coal
Semi-anthracite

NOx emissions from regenerator.

CO and CO2 formation in absorber

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 Results of fluidized bed experiments
Relationship between NOx formation in regenerator and
CO+CO2 formation in absorber. (Gao, Fuel (in press))
0.06
Fuel-N to NOx in Reg. [-]

Low-C coal High carbon coal

Conversion of fuel-N to NOx in.

Low NOx
High-C High CO+CO2
regenerator [-].

0.04

coal
Mechanism
0.02
HVB NOx reduction by
MVB
SA char in Reg. and
Linear approximation
0 transportation of
0 2 4 6
Total concentration of CO and CO in flue gas from char from to Abs.
CO+CO2 formation in absorber [%]
2
absorber [%]
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 Results of fluidized bed experiments
High-volatile coal
Low CO+CO2 from absorber
High NOx from regenerator
( Reduction of NOx in back-pass possible)

Another problem of high-volatile coal

Rapid combustion of volatile matter in O2-enriched gas
High temperature flame
Ash fusion problem

Stabilization of volatile matter combustion is required.

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Experimental (2) Volatile matter capture by
calcined limestone at elevated
temperatures using a fixed bed reactor

Porous solids can capture volatile matter at

elevated temperatures and form carbon deposit
within the pores.

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 Capacitance effect
Porous solids
V.M., tar
Pore

Carbon
Porous particles capture V.M. at high
temperatures; carbon deposit is formed
within pores.
 Increased residence time of V.M.
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 Fixed bed reactor
Step1: Evolution O２ N２
of V.M. in reactor
A. V.M. capture Reactor A

in reactor B.
Reactor B
粒子充填層
Bed material
Step2: Deposit
combustion. アルミナ担持
Pt/Al 2O3 cat.
Pt 触媒

Step3: Char Reactor C

combustion in
reactor A. CO2, CO analyzer計
CO･CO ２

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 Example of carbon deposit formation
Raw porous alumina (left) and carbon-loaded porous
alumina (right)

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Volatile matter capture by calcined limestone
Calcined limestone can capture volatile matter at
elevated temperatures and form carbon deposit.
Porous alumina MS
Calcined limestone
0.8
Carbon capture [-]

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
600 700 800 900
Temperature [oC] 16
Effect of carbon capture on VM combustion (in BFB)
Bench-scale BFB experiment A : W ater coolerd gas sampler
or suction pyrometer
Cross section:16cmx4cm
Height: 1m, Bed = 10cm h. Filter and valve

Bed temp.: 670 – 700oC A Fuel pellet

Freeboard temp.: 800oC to flue gas

analyzers
Bed materials: O 2

Right wall
Non-porous sand bed

Left wall
1 2 3 4
Porous alumina (not CaO!)
TR Dense bed
Distributor
A PE pellet (1 cm diameter, W indbox
1 cm length) was dropped
onto the bed. Air, O 2 +N 2, N 2 Air, O 2 +N 2, N 2

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Visual observation from top of BFBC during plastic
pellet combustion in non-porous sand bed
Uncontrollable flame
combustion

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 Visual observation from top of BFBC during
plastic pellet combustion in porous BM bed
Flame formation was
suppressed. Carbon
deposit combustion
was observed.

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 Conclusions
Char formation in regenerator
 Reductant of NOx in regenerator
 Source of CO and CO2 in absorber
High V.M. fuel is favorable for CO control.

However, high-volatile fuels may have a problem

of uncontrollable volatile matter combustion under
O2-enriched and high-temperature conditions.

By capturing volatile matter by porous CaO, such

problem may be solved.
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 Acknowledgements

This work is partly supported financially by

Shin-Etsu Chemical Co., Ltd.

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