synthesis of dme and gasoline from biomass-derived synthesis gas
TRANSCRIPT
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
Synthesis of DME and Gasoline
from Biomass-Derived Synthesis Gas
7th ASIAN DME CONFERENCE
November 16-18, 2011
Niigata, Japan
Ulrich Arnold, Miriam Stiefel, Ruaa Ahmad,
Herbert Lam, Manfred Döring
Karlsruhe Institute of Technology (KIT),
Institute of Catalysis Research and Technology (IKFT),
Hermann-von-Helmholtz-Platz 1,
76344 Eggenstein-Leopoldshafen
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
Dimethylether Methanol Ethanol
ETBE
Pure vegetable oil
Biodiesel
Methane
HomologationDehydrationOlefinsGasolineDiesel
Methanol-To-Olefins (MTO)
Methanol-To-Gasoline (MTG)
Methanol-To-Synfuel (MTS)
Hydrogen
MTBE
Reforming
Isobutylene
Conversion-of-Olefins-to-Distil late
Isobutylene
Transesterification of rapeseed oil with methanol
Squeezing or extraction
Fischer-Tropsch-Synthesis (FT-Synthesis)
HydroThermal Upgrading (HTU) + HydroDeOxygenation (HDO)
Hydrogen
Fermentation of sugars and starch
Degradation of (l igno)cellulose + fermentation
Anaerobic digestion
Hydrothermal gasification
Fermentation
Water gas shift reaction
Methanization
ABE-FermentationButanol
Pyrolysis
Gasification
Syngas
Pyrolyzate
Biomass
Wastes
etc.
CO, H2, CO2, H2S, COS, NH3 etc.
Direct synthesis Low temperature synthesis Direct synthesisCOD
© Ulrich Arnold
Direct gasificationBiofuels: An overview
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
GTL = Gas-To-Liquid (Syngas from natural gas) - Motunui, New Zealand (Mobil)
- Topsøe Integrated Gasoline Synthesis (TIGAS process), Texas, USA (Haldor Topsøe)
- Mobil Olefin-To-Gasoline/Distillate process (MOGD)
- Lurgi‘s Methanol-To-Synfuel process (MTS)
- CAC plant, Freiberg, Germany
CTL = Coal-To-Liquid (Syngas from coal) - Medicine Bow, Wyoming, USA (ExxonMobil)
- Jincheng, Shanxi Province, China (JAM + Uhde)
- Adams Fork Energy, Mingo County, West Virginia, USA (Uhde)
BTL = Biomass-To-Liquid (Syngas from biomass) - CHEMREC process (production of dimethyl ether, DME): Chemrec, ETC, Volvo, Delphi,
Haldor Topsøe, Preem, Total, SEA
- Choren process (Fischer-Tropsch-Technology, FT)
- French CEA project in Bure Saudron: CNIM group, Air Liquide, Choren, SNC Lavalin,
Foster Wheeler-France, MSW Energy (FT)
- BioTfueL project: Uhde Prenflo-PDQ-process, Total, IFP, French Atomic Energy Board,
Sofiproteol (FT)
- Güssing gasifier (woodchips), Oxford Catalysts (Velocys Inc., now part of the
Oxford Catalysts Group), SGC Energia (Portugal), microreactor technology (FT)
Related activities:
GTL-, CTL- and BTL-processes for fuel production
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
The bioliq® process at KIT Direct gasification CO, H , CO , H S, COS, NH etc.
Dimethylether Methanol Ethanol
ETBE
Pure vegetable oil
Biodiesel
Methane
Homologation Olefins Gasoline Diesel
M ethanol- T o- O lefins (MTO)
M ethanol- T o- G asoline (MTG)
M ethanol- T o- S ynfuel (MTS)
Hydrogen
MTBE
Reforming
Isobutylene
Isobutylene
Transesterification of rapeseed oil with methanol
Squeezing or extraction
F ischer- T ropsch-Synthesis (FT-Synthesis)
H ydro T hermal U pgrading (HTU) + H ydro D e O xygenation (HDO)
Hydrogen
Fermentation of sugars and starch
Degradation of (ligno)cellulose + fermentation
Anaerobic digestion
Hydrothermal gasification
Fermentation
Water gas shift reaction
Methanization
ABE-Fermentation Butanol
Pyrolysis
Gasification
Syngas
Pyrolyzate
Biomass
Wastes
etc.
2 2 2 3
Direct synthesis Low temperature synthesis Direct synthesis COD
© Ulrich Arnold
bioliq I
bioliq II
bioliq IV bioliq III
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
Investigated processes at KIT-IKFT
CH3OCH3 → C2H4 + H2O n CH3OCH3 → “(CH2)2n“ + n H2O
Direct Synthesis of DME Direct Synthesis of Ethanol
Syngas (H2/CO 1)
Synthesis of Olefins from DME Synthesis of Gasoline from DME
3 CO + 3 H2 → CH3OCH3 + CO2 3 CO + 3 H2 → C2H5OH + CO2
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
Focus on direct conversion of SYNGAS-TO-DME (STD)
CH3OCH3 → C2H4 + H2O n CH3OCH3 → “(CH2)2n“ + n H2O
Direct Synthesis of DME Direct Synthesis of Ethanol
Syngas (H2/CO 1)
Synthesis of Olefins from DME Synthesis of Gasoline from DME
3 CO + 3 H2 → CH3OCH3 + CO2 3 CO + 3 H2 → C2H5OH + CO2
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
● Synthesis of methanol:
2 CO + 4 H2 2 CH3OH DHR° = 182.2 kJ/mol
● Dehydration of methanol:
2 CH3OH H3COCH3 + H2O DHR° = 23.5 kJ/mol
● Water-gas shift reaction:
CO + H2O H2 + CO2 DHR° = 41.2 kJ/mol
● Total reaction:
3 CO + 3 H2 H3COCH3 + CO2 DHR° = 246.9 kJ/mol
Direct conversion of carbon monoxide-rich syngas to DME
Three reactions take place simultaneously:
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
Laboratory plant for the STD process
● Fixed bed reactor:
- Di = 1.6 cm
- L = 30 cm
- V = 60.3 cm3
● Catalyst:
Bifunctional catalyst system comprising
a methanol- and a dehydration-catalyst
● Reaction conditions:
- p = 51 bar
- T = 200 - 250 °C
- GHSV = 20 - 150 Nml/(min·gCat)
- Dilution: 70% inert gas
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
Typical results from the STD reaction
● Pressure: 51 bar
Reaction conditions: ● Temperature: 250 °C
● Space velocity: 20 - 150 Nml/(min·gCat)
● Dilution: 70% inert gas
H2/CO CO conversion (%)
DME selectivity (%)
CO2 selectivity (%)
MeOH selectivity (%)
2
61 67 32 1
1
45 66 33 1
0.67
34 65 34 1
M. Stiefel, R. Ahmad, U. Arnold, M. Döring, Fuel Process. Technol. 2011, 92, 1466-1474.
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
Influence of temperature and H2/CO ratio on DME synthesis
● Large influence of temperature on CO conversion; Optimum range: 250 - 260 °C
● CO conversion increases with increasing H2 content in the synthesis gas;
Temperature dependence decreases with decreasing H2 content
0
10
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190 200 210 220 230 240 250 260 270 280
T (°C)
CO
co
nvers
ion
(%
)
Eq
uilib
riu
m c
on
vers
ion
♦ H2/CO = 2.0
▲ H2/CO = 1.0
■ H2/CO = 0.5
p = 51 bar, 70% inert gas dilution, Vtotal = 100 Nml/min
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
● Almost maximum CO conversion at a flow rate of 50 ml/min at 250 °C
● Increase of CO conversion by increase of residence time is independent of H2/CO ratio
Influence of flow rate on DME synthesis
0
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0 50 100 150 200 250 300 350 400 450 500
V total (Nml/min)
CO
co
nve
rsio
n (
%)
p = 51 bar, T = 250 °C, 70% inert gas dilution
▲H2/CO = 0.5
■ H2/CO = 1.0
♦ H2/CO = 2.0
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
0
10
20
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0 10 20 30 40 50 60 70 80
Ar dilution (%)
CO
co
nvers
ion
(%
)
14.6%
27.4%
11.1%
♦ H2/CO = 2.0
■ H2/CO = 1.0
▲H2/CO = 0.5 p = 51 bar, T = 250 °C, Vtotal = 100 Nml/min
● The lower dilution the higher CO conversion
● The H2/CO ratio influences CO conversion:
Maximum increase was observed at H2/CO = 1
Influence of syngas dilution on DME synthesis
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
● Strong deactivation by acidic catalyst poisons within 24 h
● CO conversion decreases but DME selectivity remains constant
● Influence of NH3 is negligible within 24 h
0
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0 5 10 15 20 25
t (h)
CO
co
nvers
ion
an
d D
ME
sele
cti
vit
y (
%)
DME selectivity
CO conversion
T = 250 °C, p = 51 bar, H2/CO = 1, Vtotal = 167 Nml/min
▲ Reference; ● 146 ppm NH3; ♦ 146 ppm H2S; ■ 146 ppm HCl
Influence of catalyst poisons on DME synthesis
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
● Typical loss of activity within the first days but CO conversion remains in an
acceptable range
● DME selectivity remains constant and high during three weeks
Long-term performance of the catalyst system
in the absence and presence of CO2
0
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0 100 200 300 400 500 600 700
CO
co
nve
rsio
n a
nd
DM
E s
ele
cti
vit
y (%
)
t (h)
Gas composition:H2 = 35 mlN/min, CO = 35 mlN/min, N2 = 20 mlN/min, Ar = 27 mlN/minH2 = 35 mlN/min, CO = 35 mlN/min, N2 = 10 mlN/min, Ar = 27.5 mlN/min, CO2 = 9.5 mlN/min
DME selectivity
CO conversion
p = 51 bar, T = 250 °C, Vtotal = 117 Nml/min
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
The bioliq® process chain
Gasification (bioliq® II) Fast pyrolysis (bioliq® I)
Syngas Pyrolyzate Biomass
Methanol DME Olefins
Gasoline
HTHP gas cleaning + SYNGAS-TO-DME, STD (bioliq® III)
DME-TO-GASOLINE, DTG (bioliq® IV)
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
Dimensioning of the bioliq® process
bioliq I bioliq II bioliq IIIa+b bioliq IV
Technology: Fast pyrolysis Entrained flow gasification
bioliq IIIa:
High Temperature High Pressure (HTHP) Syngas Cleaning
bioliq IIIb:
Syngas-To-DME (STD)
DME-To-Gasoline (DTG)
Product:
Bio-slurry Synthesis gas DME Gasoline
Dimensioning: 0.5 t/h dry biomass
(2 MW)
1 t/h bio-slurry
(5 MW)
150 kg/h DME 80 kg/h gasoline
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
Fuel production within the bioliq® process
Cycle-Gas Compressor
Synthesis Gas
P-8
Waste Gas
Gasoline
Heavy
Gasoline
Product Separation
CO2-Absorber
Water-Gas Shift Reactor CO2-Absorber DME-Reactor Gasoline-Reactor
Rectification Column
Desorber
Flow chart for DME and gasoline production (bioliq® IIIb and IV)
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
bioliq® plant: View from southeast
Financial support from
bioliq® I
bioliq® II
bioliq® III
bioliq® IV
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
bioliq® plant: View from northeast
Cooperation between: and
bioliq® I bioliq® II
bioliq® III
bioliq® IV
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
Product options within the bioliq® process
Reactor 2
MeOH/DME production
Feed Reactor 1
Water-gas shift reaction
MeOH catalyst DME catalyst
Reactor 3
Gasoline synthesis
Product
+ H2
+ + MeOH
+/ + + DME
+/ + + + Gasoline
Syngas
H2:CO = 1:1
+/ + + + (Modified catalyst) Kerosene
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
● High flexibility: Production of various fuels and chemicals is possible
● High selectivity: No elaborate product separation technologies
● Processes are tunable to a large extent (catalysts, conditions, reactors etc.)
● Large optimization potential
Why the methanol/DME pathway instead of
a Fischer-Tropsch process?
Sources: ● http://nzic.org.nz/ChemProcesses/energy
● Fischer-Tropsch Technology, (Ed.s: A. Steynberg, M. Dry), Elsevier, Amsterdam, 2004.
Comparison of Fischer-Tropsch with MTG
Compound LT-FT
Co Catalyst 220 °C
HT-FT
Fe Catalyst 340 °C MTG
Methane 5 8 0.7
Ethylene 0 4 –
Ethane 1 3 0.4
Propylene 2 11 0.2
Propane 1 2 4.3
Butylenes 2 9 1.1
Butane 1 1 10.9
C5+ Gasoline 19 36 82.3
Gasoil/Distillate 22 16 –
Heavy Oil/Wax 46 5 –
Oxygenates 1 5 0.1
100 100 100
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
Conclusions
● Catalyst systems for the direct synthesis of DME in fixed bed reactors are mature
● Optimum reaction parameters are identified
● Higher H2 content in syngas increases CO conversion
● High DME selectivity (60 - 68%) even at H2/CO ≤ 1
● Main byproduct: CO2 from the water-gas shift reaction
● Low amounts of methanol (< 2%) in the product mixture;
Fast and almost complete dehydration of methanol
● Almost no further byproducts (< 0.1%);
Traces of methane, propane, propene, butane
● CO2 concentration should be low (< 5%); Otherwise significant decrease of
CO conversion
● Major challenge: Up-scaling and reactor technology
7th Asian DME Conference, November 16-18, 2011 Dr. Ulrich Arnold, IKFT
Thank you!