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153

SULPHUR #2
• In situ SO2 capture in fluidised bed combustors
• H2S control:
- low temperature processes
- the Claus process
- high temperature processes: regenerable sorbents
• Sulphur emissions from transport vehicles
see: www.hut.fi/~rzevenho
www.hut.fi/~rzevenho/
/gasbook

HELSINKI UNIVERSITY OF TECHNOLOGY ENE-47.153

Combustion of solid fuels in fluidised beds

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High temperature SO2 capture during FBC

Calcium-based sorbent Temp. 800 ~900°C

Calcined and uncalcined

Dolomite
limestone

calcination, followed by sulphation fully-calcined dolomite sulphation

CaCO3 (s) CaO (s) + CO2 CaCO3⋅MgCO3 (s) CaO (s)+ MgO (s)
CaO (s) + ½O2 + SO2 CaSO4 (s) CaO + ½O2 + SO2 CaSO4
or or
direct sulphation half-calcined dolomite sulphation
CaCO3 (s) + ½O2 + SO2 CaCO3⋅MgCO3 (s) CaCO3 (s)+ MgO (s)
CaSO4 (s) + CO2 CaCO3 (s) + ½O2 + SO2 CaSO4 (s) + CO2

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Sulphur capture in fluidised beds:

the CaCO3 calcination reaction equilibrium
0.5
0.5
CaCO
CaCO33 CaO
CaO
0.4
0.4
Pressurized
MPa

Pressurized
p(CO2),MPa

gasif
gasification
ication
0.3
0.3
Pressurized
Pressurized
p(CO2),

combustion
combustion
0.2
0.2

0.1
0.1
Atmospheric
Atmosphericprocesses
processes
00
750
750 800
800 850
850 900
900 950
950 1000
1000 1050
1050
TEMPERATURE,
TEMPERATURE,°C °C

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SO2 capture in FBC : Ca/S ratio

Bubbling (BFBC) vs. circulating (CFBC) beds

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SO2 capture in FBC

Different sorbent qualities
SORBENTS CaCO33* MgCO33* Specific Particle Particle Average
Surface Porosity Density Pore
(%wt) (%wt) ** (m²/g) (-) (kg/m³) Diameter
*** (µm)
Limestone 1 98.4 0.90 2.25 0.178 1681 0.323
Limestone 2 97.9 0.65 1.49 0.075 2416 0.251
Limestone 3 98.6 0.61 4.63 0.324 1351 0.412
Limestone 4 88.9 1.15 2.94 0.077 1762 0.209
Limestone 5 90.4 2.87 3.74 0.063 2786 0.074
Dolomite 1 60.4 32.9 0.93 0.022 2727 0.112
Dolomite 2 47.4 26.0 0.060 0.010 2855 0.291

* Chemical composition taken from Yrjas et al. (1993)

** Found from N2 BET surface measurement
*** Found from mercury penetration porosimetry

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SO2 capture in FBC

Different sorbents, 850 / 950 °C, 15 bar
11 11

(-)
(-)

CaSO4(-)
CaSO4(-)

toCaSO4
toCaSO4

0.8
0.8 0.8
0.8

CaCO3to
CaCO3to

0.6
0.6 0.6
0.6

ofCaCO3
ofCaCO3

0.4
0.4 0.4
0.4
Conversionof

Conversionof
Conversion

Conversion
0.2
0.2 0.2
0.2

00 00
00 2400
2400 4800
4800 7200
7200 9600 00 2400
9600 2400 4800
4800 7200
7200 9600
9600
Time (s)
Time (s) Time (s)
Time (s)

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Sulphur capture in FBC : product layer on dolomite

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Sulphur capture in FBC:

single particle models

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Sulphur capture in FBC : reducing zones

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Sulphur capture in FBC : effect of pressure

HELSINKI UNIVERSITY OF TECHNOLOGY ENE-47.153

Sulphur capture in FBC : 1 bar versus 15 bar

70
70
60
(%)

60
CaSO4(%)

50
50
4
ConversiontotoCaSO

40
40
30
30
Conversion

20
20
CaO (1 bar)
10 CaO (1 bar)
10 CaCO3 (15 bar)
CaCO3 (15 bar)
00
00 22 44 66 88 10
10 12
12 14
14 16
16 18
18 20
20
Time
Time(h)
(h)

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High temperature SO2 capture

(BFBC, CFBC in situ and pulverised fuel (furnace injection)

100
100
CFBC
CFBC
80
80
%
capture,%

BFBC
BFBC
Sulphurcapture,

60
60

40
Sulphur

40
PC
PC
20
20

00
00 11 22 33 44 55 66
Lime
Limeaddition
additionCa/S,
Ca/S,- -

HELSINKI UNIVERSITY OF TECHNOLOGY ENE-47.153

H2S control at low temperatures

Principle Temperature range Process names Sorbent / catalyst
Physical absorption 300 - 400 K Selexol, Rectisol, Methanol,
Sulfinol, Purisol, dimethyl ether of
product: H 2S CNG polyethylene glycol,
carbon dioxide
Chemical absorption 250 - 350 K Alkanol amines, Amines (MEA, DEA,
Girbotol, SNPA- MDEA, MGA,
product: H 2S DEA, ADIP, DIPA), potassium
Econamine carbonate
Oxidation 300 - 400 K Stretford, Solution of Na-salts
Takahax, of H 2CO 3,
product: sulphur Townsend anthraquinone-2-
sulphonic acid, . . . . .
Dry bed process ~ 300 K Iron sponge Hydrated Fe2O 3

product: sulphur

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HELSINKI UNIVERSITY OF TECHNOLOGY ENE-47.153

Chemical and
physical absorption

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H2S chemisorption process chemistry

with primary or secondary amines:
H2S + R2NH R2NH2+ + HS-
CO2 + 2 R2NH 2 R2NH2+ + R2NCOO-
CO2 + R2NH + H2O R2NH2+ + HCO3-

with tertiary amines:

H2S + R3N R3NH+ + HS-
CO2 + 2 R3N no reaction
CO2 + R3N + H2O R3NH+ + HCO3-

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H 2S
chemi-/physi-sorption
process selection

HELSINKI UNIVERSITY OF TECHNOLOGY ENE-47.153

H2S to sulphur : the Claus process

Equilibrium
Equilibrium Oxidise 1/3 of the gas flow:
conversionvs.
conversion vs.temperature
temperature 2H2O + 3O2 2SO2 + 2H2O

Recombine gas streams :

2H2O + SO2 3/x Sx + 2H2O
Overall :
2H2S + O2 2/x Sx + 2H2O

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Claus reaction process chemistry

2H 2S + O 2 2/x Sx (s) + 2H2O

Oxidation of 1/3 of the incoming H 2S and mixing it with the

rest:

2 H 2S + O2 SO2 + 2 H 2O
2 H 2S + SO2 3/x Sx (s) + 2 H 2O

Other reactions taking place, depending on the presence of CO2

and NH3:

H 2S H 2 + 1/x Sx (s)
H 2S + CO 2 H 2O + COS
COS + H 2S H 2O + CS2
2 NH3 + 3 O 2 2 NO + 3 H 2O

HELSINKI UNIVERSITY OF TECHNOLOGY ENE-47.153

H2S control by the Claus process

1.
H2S > 50%

2.
H2S
15…50%

3.
H2S
< 15%

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High temperature H2S removal: sorbents

• Sulphidation: MexOy (s) +y H2S W MexSy (s) + y H2O
• Regeneration: MexSy (s) + 1½y O2 W MexOy (s) + y SO2

Examples:
• MnO(s) + H2S W MnS (s) + H2O
• MnS (s) + 1½O2 W MnO (s) + SO2
• ZnO(s) + H2S W ZnS (s) + H2O
• ZnS (s) + 1½O2 W ZnO (s) + SO2

with, for ZnO, the following side-reactions :

• Sulphidation : ZnO (s) + H2/CO W Zn + H2O/CO2
• Regeneration : ZnS (s) + 2 O2 W ZnSO4 (s)

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H2S sorbents types and characteristics

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Temperature
ranges for
H2S sorbents

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H2S removal with regenerable sorbents

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H2S removal with calcium-based sorbents /1:

HELSINKI UNIVERSITY OF TECHNOLOGY ENE-47.153

H2S removal with calcium-based sorbents /2:

H2S and COS equilibrium pressure

High residual partial pressures for H2S and COS

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H2S removal with regenerable sorbents :

the Piñon Pine (NV) coal gasification project

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H2S removal with calcium-based sorbents :

CaS stabilisation to CaSO4

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The CaO / CaSO4 / CaS phase diagram

HELSINKI UNIVERSITY OF TECHNOLOGY ENE-4J.153

Regenerative H2S capture (with zinc titanates)

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HELSINKI UNIVERSITY OF TECHNOLOGY ENE-47.153

The Zn-O-S equilibrium

HELSINKI UNIVERSITY OF TECHNOLOGY ENE-47.153

Reactor types
for H2S
removal
from gases
with
regenerable
sorbents

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Sulphur emissions from ships

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H2S emissions from cars

Ce + SO2 + ½O2 → Ce(SO4)2

reducing
reducing
conditions
conditions

Ce(SO4)2 + 8 H2 → CeO2 + 2H2S + 6 H2O

CeO2 + 2 H2 → Ce + 2 H2O

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