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www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Coal Steam Raw Syngas
Flue gas
Heat- Pipes
Reactor
Combustion- chamber
Dipl.-Ing. Peter Treiber
Allothermal gasification and integrated syngas cleaning by hot K2CO3 scrubbing for
decentralized SNG production
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 2
Conclusion
1. Motivation: CO2freeSNG2.0 – Coal-to-SNG with integrated syngas cleaning
2. Coal/Biomass-to-SNG Allothermal gasification and carbonate syngas scrubbing
3. EVT lab-scale test stands 5 kW gasifier and Benfield scrubber
Agenda
4. Results Gasification Gasification Syngas cleaning
5. Conclusion
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 3
Conclusion
Motivation - CO2freeSNG2.0
Project goals • Integrated process optimization and economic feasibility study of
medium-scale SNG plants based on process simulations • Extensive lab- and bench-scale testing of lignite gasification with integrated
CO2 removal and catalytic methanation (5 kW Process chain) • Demonstration of the complete process chain with integrated technologies:
• 100 kW EVT-Heatpipe Reformer • Scrubbing unit based on Benfield process • Methanation with conventional and new developed catalyst systems
The research project CO2freeSNG2.0 (RFCR-CT-2013-00008) is funded by the Research Fund for Coal and Steel of the European Commission.
Motivation
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 4
Conclusion
Coal Steam Raw Syngas
Flue gas
Heat- Pipes
Reactor
Combustion- chamber
EVT – Heatpipe Reformer • Allothermal steam gasification
• Dual fluidized bed reactor:
• Atmospheric combustion
• Pressurized gasification
• Heat transfer by Heatpipes
Gasification
Vapor flow Liquid flow Mesh structure
Condensation zone
Adiabatic zone
Evaporation zone
Heat source
Heat sink
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 5
Conclusion
EVT – Heatpipe Reformer
Gasification
Gasificationfuel
Combustionfuel
Steam
Secondaryair
Combustor
Primaryair
Heatpipe reformer
Heatpipes
Gasificationreactor
Raw syngas
Flue gas
Clean syngas
Ash,char
WaterRME
Water
Ash
RME, tar, condensate
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 6
Conclusion
Integrated Syngas Cleaning Motivation • Utilization of light hydrocarbons and tars (BTX) for methanation • Removal of heavy tars to prevent coke formation • Bulk sulfur removal necessary for catalyst life time • Adjustment of the C/H/O-ratio by partial CO2 removal
Approach • Scrubbing at elevated temperature based on Benfield process
• Condensation of heavier tars • Bulk removal of sulfur components • Removal of surplus CO2
Application • Bulk syngas cleaning for decentralized SNG production in small and mid scale plants
Syngas cleaning
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 7
Conclusion
Carbonate Scrubbing – Benfield Process
Basic data Carbonate scrubbing • Increased solvent temperature • No additional solvent cooling before absorber
inlet • Low reboiler duty (steam) necessary • Stabile and non-toxic solvent
Pump
Lean CarbonateSolution
Valve
CO2-free Gas
RawGas
120°C
Level Control
Reflux
CO2
Rich CarbonateSolution
115°C
Abso
rber
(10.
..20
bar)
Rege
nera
tor (
0,5 .
..1 b
ar)
Cond
ense
r
Steam
𝐾2𝐶𝐶3 + 𝐶𝐶2 + 𝐻2𝐶 ⇌ 2 𝐾𝐻𝐶𝐶3 𝐾2𝐶𝐶3 + 𝐻2𝑆 ⇌ 𝐾𝐻𝑆 + 𝐾𝐻𝐶𝐶3
Homer E. Benson Joseph H. Field
….
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 8
Conclusion
SNG-Production – process chain 5 kW
Air H2O
A
Gas control rig
Gasifier
Carbonate Scrubber
Hot gas cleaning
Raw Syngas
Humidifier
350 °C1-4 bar
–
– 0 – 350 °C
Fuel N2
Test stands
H2O
Absorber Desorber
Carbonate Scrubber
Hot gas cleaning
p
KHCO3
Clean SyngasRaw Syngas
350 °C1-4 bar
250 – 400 °C
–
100 – 120 °C0 – 350 °C
CO2
N2
Desorber
polytropicMethanation
3
Clean Syngas
Gasanalysis
SNG
+20 °C -20 °C
250 – 400 °C
230 – 250 °C
– 120 °C
CO2Condenser
µ-GC
Tar protocol
SPE
GA
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 9
Conclusion
SNG-Production – 5 kW Gasifier
Steam
Fuel
Raw Syngas
Technical Data
• Stationary fluidized bed
• Electrical reactor heating
• Allothermal steam gasification
• Pressure: up to 6 bara
• Gasification temperature: 800 – 900 °C
• Hot gas filter
• Inspection glas
Reactor heating
Fuel inlet Pressure lock
Steam generator
SPC
Lignite Biomass
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 10
Conclusion
SNG-Production – 5 kW Scrubber
Technical Data • P = 5 bara , TSolvent = 100°C, 30 wt.-% K2CO3
• Packings: Raschig Rings 6 mm VA
Test stands
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 11
Conclusion
Results – Gasification – Temperature
Biomass gasification p = 1.3 bara σ = 12
Results
0%
10%
20%
30%
40%
50%
60%
800 810 820 830 840
Syng
as c
ompo
sitio
n (d
ry, N
2-fr
ee)
Fluidized bed temperature [°C]
H2
CO2
CO
CH4
b)
a)
b)
c)
U/U0 = 1.5
U/U0= 3
U/U0= 6
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 12
Conclusion
1
10
100
1,000
10,000
Syng
as ta
r loa
ding
(dry
, N2-
free
) [m
g/N
m³]
814°C WS
820°C WS
829°C WS
835°C WS
Results – Gasification – Temperature
Biomass gasification p = 1.3 bara σ = 12
Results
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 13
Conclusion
0%
10%
20%
30%
40%
50%
60%
0 3 6 9 12 15
Syng
as c
ompo
sitio
n (d
ry, N
2)-fr
ee)
Stoichiometric steam ratio σ [-]
H2
CO2
CO
CH4
b)
Results – Gasification – Steam excess ratio
Results
Biomass gasification p = 1.3 bara 𝑇𝐹𝐹 = 830 °C
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 14
Conclusion
1
10
100
1,000
10,000Sy
ngas
tar l
oadi
ng (d
ry, N
2-fr
ee) [
mg/
Nm
³]Sigma 4Sigma 6Sigma 8Sigma 10Sigma 12
Results – Gasification – Steam excess ratio
Results
Biomass gasification p = 1.3 bara 𝑇𝐹𝐹 = 830 °C
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 15
Conclusion
0
4
8
12
16
20
0
400
800
1,200
1,600
2,000
820 825 830 835 840
Thiop
hene
[ppm
]
H 2S
[ppm]
Fluidized bed temperature[°C]
H2S
Thiophene
Results – Gasification p = 5,2 bara, σ = 3,26
Results
Light Hydrocarbons and Sulfur
• Overall tar reduction with rising gasification temperature
• At lower gasification temperatures shift towards aromates
• Ethene and Ethine decrease with rising gasification temperature
• Sulfur compounds barely affected by fluidized bed temperature
• H2S
• Thiophene
0.00
0.05
0.10
0.15
0.20
0.25
820 825 830 835 840
C xH y
conc
entra
tion [
Vol.-%
]
Fluidized bed temperature [°C]
Ethene
Ethine
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 16
Conclusion
0
10
20
30
40
50
60
70
80
90
100
CO2 H2S
Rem
oval
effi
cien
cy [%
]
Results – Scrubber
Results
L/G = 14
L/G = 10
Simulation vs. bench scale tests • Simulation of 90% CO2 removal efficiency @ L/G 19 proofed only up to 65% in bench scale
tests due to heat losses and edge effects → higher efficiency reached in pre-pilot scale
Removal efficiency
𝜂𝐶𝐶2 =(𝑥𝐶𝐶2,𝑟𝑟𝑟 − 𝑥𝐶𝐶2,𝑐𝑐𝑐𝑟𝑐)
(𝑥𝐶𝐶2,𝑟𝑟𝑟 × (1 − 𝑥𝐶𝐶2,𝑐𝑐𝑐𝑟𝑐)
𝜂𝐻2𝐻 =(𝑥𝐻2𝐻,𝑟𝑟𝑟 − 𝑥𝐻2𝐻,𝑐𝑐𝑐𝑟𝑐)
(𝑥𝐻2𝐻,𝑟𝑟𝑟 × (1 − 𝑥𝐻2𝐻,𝑐𝑐𝑐𝑟𝑐)
Liquid-to-Gas ratio
𝐿𝐺
= �̇�𝐻𝑆𝑐𝑆𝑐𝑐𝑆�̇�𝐻𝑆𝑐𝑆𝑟𝑆
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 17
Conclusion
Results – Scrubber – L/G-ratio
Results
0%
10%
20%
30%
40%
50%
60%
70%
0%
10%
20%
30%
40%
50%
60%
70%
RawSyngas
10 12 14 16 18 20
CO2
Rem
oval
effi
cien
cy
Syng
as c
ompo
sitio
n (d
ry, N
2-fr
ee)
Liquid-to-gas ratio L/G [-]
H2
CO2
CH4
CO
CO2 Removal efficiency
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 18
Conclusion
1
10
100
1,000
10,000
Syng
as ta
r loa
ding
[mg/
Nm
³]GasifierL/G 10L/G 12L/G 14L/G 16L/G 18L/G 20
Results – Scrubber – L/G-ratio
Results
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 19
Conclusion
Results – Scrubber – Solvent
Results
0%
10%
20%
30%
40%
50%
60%
70%
80%
8 10 12 14 16 18 20 22
CO2
Rem
oval
effi
cien
cy
Liquid-to-gas ratio L/G [-]
10 wt.-% K2CO3
20 wt.-% K2CO3
30 wt.-% K2CO3 ** Biomass
gasification K2CO3
K2CO3
K2CO3
a)
0%
10%
20%
30%
40%
50%
60%
70%
80%
8 10 12 14 16 18 20 22CO
2Re
mov
al e
ffici
ency
Liquid-to-gas ratio L/G [-]
Without PZ
2.5 wt.-% PZ
5.0 wt.-% PZ
b)
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 20
Conclusion
Results – Scrubber
Results
0
500
1000
1500
2000
2500
3000
3500
Gasifier Scrubber
Tar c
once
ntra
tion
[mg/
Nm
³] (S
PE-M
etho
d)
BTX
Aromates
Tar removal
• Reduced syngas vol.-flow due to CO2 removal
• Higher BTX concentration after scrubber but • Less aromates after scrubber
• Close to total removal of heavier hydrocarbons
(TB > 350 °C)
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 21
Conclusion
100 kW Process chain
Desorber Absorber
Condenser
Flash drum
Reboiler
Tar separator
HPR filter
EVT-Heatpipe Reformer Pre-pilot carbonate scrubber
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 22
Conclusion
100 kW Process chain – Demonstration
0
10
20
30
40
50
60
70
0 20 40 60 80 100
120
140
160
180
200
220
240
260
Syng
asco
mpo
sitio
n(d
ry, N
2-fr
ee) [
vol.-
%]
Time [min]
H2
CO
CO2
CH4
Fuelstop
H2
CH4
CO2
CO
Heatpipe ReformerScrubbernot recorded (methanation)
123
1 1 12 23 3
H2
COCO2
CH4
𝜂𝐶𝐶2= 60 %
Lignite gasification pgasifier = 4,0 bara pabsorber = 3,8 bara TSyngas, clean = 120 °C
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 23
Conclusion
100 kW Process chain – Demonstration
pre-pilot scrubber at FAU
0
10
20
30
40
50
60
70
H2 CO CO2 CH4
Conc
entr
atio
n (d
ry, N
2-fr
ee) [
vol.-
%] Lignite 1.3 bar
Lignite 4.0 bar
Biomass 1.5 bar
Biomass 4.0 bar
www.evt.cbi.fau.de Department Chemie- und Bioingenieurwesen (CBI) Lehrstuhl für Energieverfahrenstechnik Prof. Dr.-Ing. Jürgen Karl
1. Deutsches Doktorandenkolloquium Bioenergie, DBFZ, September 20-21, 2018, Leipzig
Motivation
Gasification
Syngas Cleaning
Test stands
Results
Folie 24
Conclusion
Conclusion CO2freeSNG2.0 • Decentralized SNG-Production from coal or biomass with
integrated syngas cleaning and CO2-removal • Bench scale testing: Gasifier, Scrubber, Methanation (5 kW) • Demonstration of the pre-pilot scale process chain
• Heatpipe Reformer(100 kW) + Scrubber
Allothermal steam gasification • Steam surplus variation to support methanation • Tar load and composition in focus of investigation Integrated Syngas Cleaning • Syngas scrubbing at elevated temperatures based on the
Benfield process as bulk cleaning process • Heavy tar components (Condensation) • Surplus CO2 und sulfur compounds removal
• Utilization of light hydrocarbons in Methanation
Conclusion