comparative study of steam co-gasification of hard coal ... aten… · comparative study of steam...
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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)
U.S. DOE, International Energy Outlook 2010. Washington, IEA.
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.
U.S. DOE, International Energy Outlook 2010. Washington, IEA.
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
Gasification process
Coal
Hydrogen
Gasification with Hydrogen
C + 2H2 = CH4
Gasification with Hydrogen
CO + 3H2 = CH4 + H2O Exothermic reaction
Exothermic reaction
Gasification process
(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
1 - Salix Viminalis, 2 Andropogon Gerardi, 3 - Helianthus Tuberosus, 4 - Sida Hermaphrodita, 5 - Miscanthus X Giganteus,
6 - Spartina Pectinata
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
1 - Salix Viminalis, 2 Andropogon Gerardi, 3 - Helianthus Tuberosus, 4 - Sida Hermaphrodita, 5 - Miscanthus X Giganteus,
6 - Spartina Pectinata
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.
Co-gasifiaction of hard coal and energy crops
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
1 - Salix Viminalis, 2 Andropogon Gerardi, 3 - Helianthus Tuberosus, 4 - Sida Hermaphrodita, 5 - Miscanthus X Giganteus,
6 - Spartina Pectinata
Sample no
Chan
ge
in
to
tal ga
s y
ield
[%
]
Co-gasifiaction of hard coal and energy crops
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
1 - Salix Viminalis, 2 Andropogon Gerardi, 3 - Helianthus Tuberosus, 4 - Sida Hermaphrodita, 5 - Miscanthus X Giganteus,
6 - Spartina Pectinata
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
[%
]
Co-gasifiaction of hard coal and energy crops
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
1 - Salix Viminalis, 2 Andropogon Gerardi, 3 - Helianthus Tuberosus, 4 - Sida Hermaphrodita, 5 - Miscanthus X Giganteus,
6 - Spartina Pectinata
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