Comparative study of steam co-gasification of hard coal ... ATEN… · Comparative study of steam co-gasification of hard coal and biomass (Spartina pectinata and Miscanthus X Giganteus

Comparative study of steam co-gasification of hard coal and biomass (Spartina pectinata and Miscanthus X Giganteus)

focused on hydrogen-rich gas production

Adam SmolińskiNatalia Howaniec

Central Mining InstituteDepartment of Energy Saving and Air Protection

Plac Gwarków 1, 40-166 Katowice, PolandE-mail: [email protected]

Aim

Experimental demonstration

of advantages of coal and biomass

co-gasification

Outline

1. Role of coal in energy security

2. Coal and biomass gasification vs. coal & biomass co-gasification to hydrogen-rich gas

3. Synergy effects observed in coal &biomass co-gasification

CENTRAL MININGINSTITUTE (GIG)is a research and

development organization related to the Upper

Silesian mining industry and region since 1945

The Experimental Mine “Barbara”

in Mikołów was established

20 years earlier and now is a part of Central

Mining Institute

Poland, 40-166 Katowice, Plac Gwarków 1

http://www.gig.eu

The Institute’s activities have been always devoted to the most essential occupational safety problems, development of mining technologies and techniques, and environmental protection against the effects of industrial activity, particularly related to the mining sector.

The results of scientific and research work performed at the Institute create the foundation of a modern and safe Polish mining, and numerous solutions has found application in the mining industries all over the world.

ACTIVITIES OF THE CENTRAL MINING INSTITUTE (GIG)

BASIC ACTIVITY AREAS OF GIG

METHODS OF SIMULATION AND ASSESSMENT OF TECHNOLOGIES USING COMPUTER TECHNIQUES

MINING AND GEOENGINEERING

TECHNOLOGIES OF SUSTAINABLE DEVELOPMENT IN THE FIELD OF ENVIRONMENTAL ENGINEERING

INDUSTRIAL SAFETY

MATERIAL ENGINEERING FOR THE NEEDS OF EXTRACIVE INDUSTRY

CERTIFICATION, CONFORMITY ASSESSMENT AND MANAGEMENT SYSTEMS

SUSTAINABLE POWER PRODUCTION TECHNOLOGIES BASED ON SOLID FOSSIL FUELS AND RENEWABLE ENERGY RESOURCES

ECONOMIC AND SOCIAL STUDIES

EDUCATION

BASIC ACTIVITY AREAS OF GIG

SUSTAINABLE DEVELOPMENT STRATEGIESIN REGIONAL FRAMES

World marketed energy consumption 1990-2035

0

200

400

600

800

1990 1995 2000 2007 2015 2020 2025 2030 2035

quadrillion Btu

ProjectionsHistory

355374

406

495

1 Btu (British thermal unit) =1055.0559 J U.S. DOE, International Energy Outlook 2010. Washington, IEA.

0

10

20

30

40

2007 2015 2020 2025 2030 2035

Nuclear

Renewables

Natural gas

Coal

Liquids

trillion kWh

Electricity generation by fuel 1990-2035

U.S. DOE, International Energy Outlook 2010. Washington, IEA.

World net electricity generation is expectedto increase by 87%from 18.8 trillion kWh in2007 to 25.0 trillion kWh in 2020 and 35.2 trillionkWh in 2035.

Coal share in electricity generation will remain on the level of above 40%.

World coal consumption is assumed to increase by 1.6 percent peryear on average from 2007 to 2035.

Coal share of world energy consumption by sector

Coal share in world energy consumption (27% in 2007, 28% in 2035) and in electricity generation (44% in 2007, 43% in 2035) is stable.

Worldcoal consumption is expected to increase by 56%, from 132x1024 Btu in 2007 to 206x1024 Btu in 2035.

0

10

20

30

40

50

Electricity Industrial Other sectors Total

2007 2020 2035

(percent)


0

10

20

30

2007 2015 2020 2025 2030 2035

OECD Non-OECD

(billion metric tons)

World energy-related CO2 emissions

World energy-related CO2 emissions are expected to growfrom 29.7 billion metric tons in 2007 to 33.8 billion metrictons in 2020 and 42.4 billion metric tons in 2035.


Coal resources

Diversification of coal applications

Is coal a clean fuel?

Coal processing

14

Clean Coal Technologies +

CO2 Sequestration

Green energy from coal

15

Main trends in coal processing

• Combustion

• Gasification

• Polygeneration

• Hydrogenation

16

Products of coal processing

Coal

Gasification Hydrogenation

Fischer-Tropsch

synthesis

Methanol Synthesis

Methanation Refinery Treatment

Liquid Fuels

Chemicals Methanol SNG Liquid Fuels

Combustion

Gas combustion

Power and Thermal energy

Separation

Hydrogen

Coking

Coke

Coal

Oxygen

Gasification with Oxygen

C+1/2O2=CO

C + O2 = CO2

Gasification with Carbon Dioxide

C+CO2=2CO

Exothermic reaction

Endothermic reaction

Gasification process

Coal

Steam

Gasification with Steam

C + H2O = CO + H2

Water-Gas Shift

CO + H2O = H2 + CO2 Exothermic reaction

Endothermic reaction


Coal

Hydrogen

Gasification with Hydrogen

C + 2H2 = CH4

Gasification with Hydrogen

CO + 3H2 = CH4 + H2O Exothermic reaction

Exothermic reaction


(volume %)H2 25-30CO 30-60CO2 5-15H2O 2-30CH4 0-5

H2S 0,2-1COS 0-0,1N2 0,5-0,4Ar 0,2-1NH3 0-0,3

Ash/Slag

Gasif

icati

on

of

co

al

Further Processing

Typical gasifiergas composition

Gasification methods

• In a fixed bed (quasi-stationary)Sasol - Lurgi FBDB

• In a fluidized bedHigh Temperature Winkler (HTW) gasification

technology

• In a stream reactorSHELL, GE-TEXACO

Industrial gasification plantscapacities by fuel type

NETL: 2010

Worldwide

Gasification

Database

NETL: 2010 Worldwide Gasification Database

Industrial gasification plants by region

NETL: 2010 Worldwide Gasification Database

Industrial gasification plantsby gasifier technology

IGCC Buggenum

NOX emissions are typically below 10 ppm. Sulfur removal efficiency is over 99%. This results in total emissions of sulfur dioxide and NOX

being less for operation on syngas produced from coal than natural gas. Particulate emissions including fly ash, chlorides and heavy metals are virtually zero [http://www.netl.doe.gov/technologies/coalpower/gasification/gasifip

edia/6-apps/6-2-6-4_nuon.html].

Efforts of co-gasification of up to 50% w/w of biomass were undertaken to generate a high proportion of “green” energy. This was in response to the plants obligations resulting from signing the Kyoto protocol by the Netherlands to make a CO2 emission reduction of 200,000 t/year, which is equivalent to 28-50 MWe derived from biomass.Prins MJ, Ptasinski KJ, Janssen FJJG. From coal to biomass gasification: Comparison of thermodynamic efficiency. Energy 2007;32:1248–1259.

van Dongen A, Kanaar M. Co-gasification at the Buggenum IGCC power plant. DGMK-Fachbereichstagung „Energetische Nutzung von Biomassen“ vom 24.

bis 26. April 2006. http://www.dgmk.de/kohle/abstracts_velen7/Dongen_Kanaar.pdf.

Hydrogen-rich gas production through coal gasification

The efforts of the world research activities in the fieldof CCT development focus to a considerable extend

on the development of integrated hydrogen and power generation technologies, based on coal gasification

process.

Synthesis gas Hydrogen

Coal

� Resources

� Gasification technology

� Environmental aspects

of coal processing

Energy crops

� Resources

� Gasification technologies

� Environmental aspects of

biomass processing

Coal & biomass co-gasification:

� Resources

� Co-gasification technologies

� Environmental aspects

Area of research activities in the field of coal and biomass gasification and co-gasification

R&D activities in the field of gasification

Thermodynamic analysis, optimization: influence of various operating parameters on the yield and

composition of gas: various gasification agents, temperature, pressure, metal oxides as catalysts

and various reactor types.

Carbonaceous fuel:

coal and biomass

Syngas

Electricity and thermal energy

Chemical synthesis: SNG, methanol, ammonia, liquid fuel

Fuel cells

Petrochemical industry

Chemical industry

Hydrogen

Coal & biomass co-gasification

Synergy effect in co-gasification

Area of research activities in the field of coal and biomass gasification and co-gasification

Smoliński A., Coal char reactivity as a fuel selection criterion for coal-based hydrogen-rich gas production in the process of steam gasification, Energy Conversion and Management, 52 (2011), 37-45

Experimental procedure

Experimental Procedure

Experimental Procedure

• Testing of coal/biomass chars reactivity as a fuel selection criterion for coal/biomass-based hydrogen-rich gas production in the process of steam co-gasification.

• Comparison of biomass, lignite and hard coal in the process of steam gasification.

• Coal & biomass steam co-gasification.

Experimental procedure

Materials

Salix viminalis

Sida hermaphrodita

Spartina pectinata

Miscanthus X giganteus

Andropogon gerardi

17 hard coal samples from various Polish coal mines3 lignite samples from different Polish opencastsconsidered to be potential future suppliers of coal for full scale gasification in

terms of resources and price.

Helianthus tuberosus

Table 1. Physico-chemical parameters determined for biomass samples.

Materials

35.5835.7331,2725,5435,7135,29Oxygen O[%]

<0.01<0.01<0.01<0.01<0.01<0.01Nitrogen N[%]

5.625.686,597,575,646,22Hydrogen Ht [%]

45.7747.1853,7153,3046,6252,19Carbon Ct [%]

0.120.040,050,060,040,05Total sulfur St [%]

154811503014942142421454316697Calorific value Qi [kJ/kg]

169201648416546161321598918171Heat of combustion Qs[kJ/kg]

69.8971.4776,0070,2669,2473,16Volatiles V [%]

4.312.631,603,873,181,51Ash A [%]

8.698.766,789,728,814,74Total moisture W [%]

Spartinapectinata

Sidahermaphro

-dita

Miscanthus X

Giganteus

Andropogon gerardi

Helianthus tuberosus

Salix Viminalis

Parameter/biomass samples

0,00

0,20

0,40

0,60

0,80

1,00

1,20

1,40

1,60

0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70

O/C

H/C

lignite

hard coal

biomass

Materials

Fig.1 Atomic ratios H/C and O/C of tested samples.

Howaniec N., Smoliński A., Steam gasification of energy crops of high cultivation potential in Poland to hydrogen-rich gas, International Journal of Hydrogen Energy, http://dx.doi.org/10.1016/j.ijhydene.2010.11.049

Selection of optimal fuel for hydrogen-rich gas production

• Reactivity, as a factor determining

the coal/biomass suitability for hydrogen

production.

• The reactivity of coal/biomass char

in gasification process determines

the reaction rate between coal/biomass

char and gasification agent.

The reactivity tests are conducted using:

• Thermogravimetric analyzers (TGA)

• Field’s Drop Tube Reactors (DTR)

• Fixed Bed Reactors

• Fluidized Bed Reactors (FBR)

• Calorimetric Bombs

• Wire Mesh Reactors (WMR)

• Hot Rod Reactors (HRR)

How to test the reactivity?

Methodology of determining coal/biomass char reactivity

The sample of 3g of coal/biomass is fed into the vertical fixed bed gasifier and the reactor is heated in an inert gas atmosphere to the temperature of 700, 800 or 900oC. After temperature stabilization steam is injected upward to the gasifier with a flow rate of 3.2 mL/min. The outlet gas is cooled and dried in a water trap and then analyzed on-line with a GC. Gas analyses are performed every 3.2 min and the amount of gas produced in the gasification process is measured with a flow meter.

Smoliński A., Gas chromatography as a tool for determining coal chars reactivity in a process of steam gasification, ActaChromatographica, 20(3) (2008) 349-365

Coal/biomass chars reactivity for 50% of carbon conversionand the maximum reactivity

X -% of carbon conversionm0 - the initial carbon content in a samplem - the time dependent carbon content in the gaseous products mixturetx - time required to achieve carbon conversion of X%

[ ]1

x0

Xs

dt

dm

m

1R

−⋅= [ ]% 100

m

mX

0

⋅=

Fig.2 Chromatogram of a synthesis gas obtained in the process of steam gasification of a coal sample from Piast coal mine: a) the column PLOT U and b) the analytical column MS5A PLOT

min0.5 1 1.5

µV

2000

03

000

0

0.9

00

TCD1 A

a)

min0.5 1 1.5

µV

2000

03

000

0

0.9

00

TCD1 A

a)

min0.5 1 1.5 2µ

V0

10

000

2000

0

*0.6

73

*1.1

01

*1.7

23

*2.2

41

TCD2 A

b)

min0.5 1 1.5 2µ

V0

10

000

2000

0

*0.6

73

*1.1

01

*1.7

23

*2.2

41

TCD2 A

b)

Experimental results of coal/biomass char reactivity tests

Fig.3 a) Main gaseous products flows and b) percentage composition of the gaseous

product mixture in the process of steam gasification of the coal sample from Piast coal mine

Sample no. 1

0%

20%

40%

60%

80%

100%

0

192

384

576

768

960

1152

1344

1536

1728

1920

2112

2304

2496

2688

2880

3072

3264

3456

t [s]

C [

% v

ol.] CH4

CO

CO2

H2

Sample no. 1

0

0,5

1

1,5

2

2,5

3

0

192

384

576

768

960

1152

1344

1536

1728

1920

2112

2304

2496

2688

2880

3072

3264

3456

3648

t [s]

Q [

ml/s]

H2

CO2

CO

CH4

Experimental results of coal/biomass char reactivity tests

0

1

2

3

4

5

6

7

8

1 2 3 4 5 6 7 8 9 10 11 12

Sample no

R50,

Rm

ax *

10-4

(1/s

)

R50

Rmax

0

500

1000

1500

2000

2500

1 2 3 4 5 6 7 8 9 10 11 12

Sample no

t50, tm

ax (s)

t50

tmax

a) b)

0

1

2

3

4

5

6

7

8

1 2 3 4 5 6 7 8 9 10 11 12

Sample no

R50,

Rm

ax *

10-4

(1/s

)

R50

Rmax

0

500

1000

1500

2000

2500

1 2 3 4 5 6 7 8 9 10 11 12

Sample no

t50, tm

ax (s)

t50

tmax

a) b)

wb1 wb2 wb3 wk1 wk2 wk3 wk4 wk5 SP HT SH MXG wb1 wb2 wb3 wk1 wk2 wk3 wk4 wk5 SP HT SH MXG

Fig.4 a) Lignite, hard coal and biomass chars reactivities in steam gasification at 700oC

for 50% of carbon conversion, R50, and the maximum reactivity, Rmax, and b) times needed to reach the reactivities, t50, and tmax, respectively.

•wb1-wb3 – lignite samples•wk1-wk-5 – hard coal samples•SP,HT,SH, MXG – biomass samples

Howaniec N., Smoliński A., Stem gasification of energy crops pf high cultivation potential in Poland to hydrogen rich gas, International Journal of Hydrogen Energy, 38 (2011) 2038-2043.

Experimental results ofcoal/biomass char reactivity tests

Fig.5 a) Total volume and b) percentage composition of synthesis gas generated in 1-h tests of steam gasification calculated per 1 kg of lignite (samples nos 1-3), hard coal(samples nos 4-8) and biomass (samples nos 9-12) at 700oC.

•wb1-wb3 – lignite samples•wk1-wk-5 – hard coal samples•SP,HT,SH, MXG – biomass samples

Comparative experimental study of biomass, lignite and hard coal steam gasification

0

500

1000

1500

2000

2500

1 2 3 4 5 6 7 8 9 10 11 12

Sample no.

To

tal

gas v

olu

me (

dm

3)

0

10

20

30

40

50

60

70

80

1 2 3 4 5 6 7 8 9 10 11 12

Sample no.

C (

%vo

l.) CO2

H2

CO

CH4

a) b)

0

500

1000

1500

2000

2500

1 2 3 4 5 6 7 8 9 10 11 12

Sample no.

To

tal

gas v

olu

me (

dm

3)

0

10

20

30

40

50

60

70

80

1 2 3 4 5 6 7 8 9 10 11 12

Sample no.

C (

%vo

l.) CO2

H2

CO

CH4

a) b)

wb1 wb2 wb3 wk1 wk2 wk3 wk4 wk5 SP HT SH MXG wb1 wb2 wb3 wk1 wk2 wk3 wk4 wk5 SP HT SH MXG

Smoliński A., Howaniec N., Stanczyk K., A comparative experimental study of biomass, lignite and hard coal steam gasification, Renewable Energy, 36 (2011), 1836-1842.

Steam co-gasification of hard coal and biomass at the temperatures of 700, 800 and 900oC

Fig.6 a) The main gaseous products flows and b) the percentage composition of the gaseous product mixture obtained in the process of steam co-gasification of hard coal and Spartina pectinata (20%w/w) at 900oC

Spatina pectinata 20%w/w (900C)

0

10

20

30

40

50

60

70

80

90

100

0 3 6 10 13 16 19 22 26 29 32 35 38 42 45 48 51 54 58 61

t [min]

C[%

ob

j.]

CH4

CO

CO2

H2

Spartina pectinata 20%wag. (900C)

0

100

200

300

400

500

600

0 3 6 10 13 16 19 22 26 29 32 35 38 42 45 48 51 54 58 61

t [min]

Q [

ml/

min

] H2

CO2

CO

CH4

700C

0,00

2,00

4,00

6,00

8,00

10,00

12,00

14,00

1 2 3 4 5 6

Nr badanej biomasy

Zm

ian

a o

bję

tości w

od

oru

, %

20%w ag. 40%w ag. 60%w ag. 80%w ag.

Co-gasifiaction of hard coal and energy cropsHydrogen yield increase in the process of co-gasification of hard coal from coal

mine Piast and biomass at the temperature of 700oC to gasification process

1 - Salix Viminalis, 2 Andropogon Gerardi, 3 - Helianthus Tuberosus, 4 - Sida Hermaphrodita, 5 - Miscanthus X Giganteus,

6 - Spartina Pectinata

Hyd

rogen

yie

ld in

cre

ase

[%

]

Sample no

Co-gasifiaction of hard coal and energy cropsHydrogen yield increase in the process of co-gasification of hard coal from coal mine Piast and biomass at the temperature of 800oC compared to gasification

process



800C

0,00

2,00

4,00

6,00

8,00

10,00

12,00

14,00

16,00

1 2 3 4 5 6

Nr badanej biomasy

Zm

ian

a o

bję

tości w

od

oru

, %

20%w ag. 40%w ag. 60%w ag. 80%w ag.

Hyd

rogen

yie

ld in

cre

ase

[%

]

Sample no

Co-gasifiaction of hard coal and energy crops

Hydrogen yield increase in the process of co-gasification of hard coal from coal mine Piast and biomass at tha temperature of 900oC compared to gasification process

900C

0,00

2,00

4,00

6,00

8,00

10,00

12,00

14,00

16,00

1 2 3 4 5 6

Nr badanej próbki

Zm

ian

a o

bję

tości w

od

oru

, %

20%w ag. 40%w ag. 60%w ag. 80%w ag.

Hyd

rogen

yie

ld in

cre

ase

[%

]

Sample no



700C

0

1

2

3

4

5

6

7

8

1 2 3 4 5 6

Nr badanej biomasy

Zm

ian

a o

bję

tości g

azu

, %

20%w ag. 40%w ag. 60%w ag. 80%w ag.


Change in total gas yield in co-gasification of hard coal from coal mine Piast and biomass at the temperature of 700oC compared to gasification process



Sample no

Chan

ge

in

to

tal ga

s y

ield

[%

]





800C

-1

1

3

5

7

9

11

1 2 3 4 5 6

Nr badanej biomasy

Zm

ian

a o

bję

tości g

azu

, %

20%w ag. 40%w ag. 60%w ag. 80%w ag.

Sample no

Chan

ge

in

to

tal ga

s y

ield

[%

]





900C

0

1

2

3

4

5

6

7

8

9

10

1 2 3 4 5 6

Nr badanej biomasy

Zm

ian

a o

bję

tości g

azu

, %

20%w ag. 40%w ag. 60%w ag. 80%w ag.

Sample no

Chan

ge

in

to

tal ga

s y

ield

[%

]

• Co-gasification of coal and biomass may be considered as contributing to CO2 emission reduction, when compared to fossil fuel gasification, since biomass is claimed to be carbon neutral (CO2 emitted in gasification process is balanced by the amount captured from the atmosphere in the process of photosynthesis).

• Hydrogen content in a product gas increased with an increase in process temperature for all biomass/coal ratios.

• A synergy effect was observed in co-gasification tests for blends of 40% w/w content of biomass, consisting in an increase in the volume of product gas and hydrogen content, when compared to the tests of coal and biomass gasification.

Conclusions

Thank you for your attention

Documents

Comparative study of steam co-gasification of hard coal ... ATEN… · Comparative study of steam co-gasification of hard coal and biomass (Spartina pectinata and Miscanthus X Giganteus