refuels – raw materials, processes and applications for ......synthesis of fuels and fuel...
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KIT – The Research University in the Helmholtz Association
Institute of Catalysis Research and Technology (IKFT)
www.kit.edu
refuels – Raw Materials, Processes and Applications for Synthetic Fuels
Ulrich Arnold, Kathrin Hackbarth, Philipp Haltenort, Jörg Sauer
COMSYN European 2nd Generation Biofuels - Opportunities and Applications 1st Workshop of the European Project COMSYN German Aerospace Center (DLR) Stuttgart - INERATEC GmbH and KIT Karlsruhe, April 18-19, 2018
Institute of Catalysis Research and Technology (IKFT) 2 19.04.2018
Content
Legislative background
Technological background
OME fuels • Molecular structure & fuel properties • OME synthesis: State of the art • Comparison of OME production processes
• Current work
Challenges
Summary & outlook
Institute of Catalysis Research and Technology (IKFT) 3 19.04.2018
Legislative background (I)
-23%
-43%
-36%-2%
-18%
-69%
-62%
-66%
-51%
-42%
-34%
-87%0
50
100
150
200
250
300
350
400
450
500
Energy sector Households Industry Transport Agriculture others
Tota
l em
issio
n pe
r sec
tor i
n Ge
rman
yin
Mio
. t C
O2-
Equi
vale
nt
1990
2014
Target 2030*
Target 2050 (-95%)
*upper target value©DBFZ 12/2016 based on Climate protection plan of German Federal Government 11/2016
Main driver for biofuel activities in Germany: Climate protection by low-carbon technologies, CO2 use and efficient renewable fuels and products from biomass and electricity
Institute of Catalysis Research and Technology (IKFT) 4 19.04.2018
Legislative background (II)
Topic EU Directives Energy Carrier • Renewable energy mandates
Fixed in RED 2009/28/EG with 10% RE in 2020 and FQD with 6% CO2-eq reduction by 2020; No sector-related targets for post-2020 (1990-2030: −40% GHG, 27% renewable energies, 27% improvement of energy efficiency)
• Legislation for renewable fuels
RED: 7% cap for biofuels based on food crops, i/dLUC, sustainability criteria and methodology for GHG, min. 60% GHG reduction for new plants
• Taxes for fuels Energy Taxation Directive (ETD)
Energy Infrastructure
Clean Power for Transport Directive (CPD) Alternative Fuels Infrastructure Directive (AFID)
Vehicles • Legislation for vehicle emission standards
CO2 regulations 2020 on tank-to-wheel basis, fleet averages for manufacturers: 95 g/km passenger cars / 120 g/km for HDV EURO VI emission regulations for HC, CO, NOx, PM
• Incentives for low emission vehicles
Individual incentives for EU member countries
Institute of Catalysis Research and Technology (IKFT) 5 19.04.2018
- Biomass, residues, wastes
- Coal, natural gas, oil
- CO2
- Pyrolysis- Gasification- Reforming- Reduction
Synthesis gas Methanol
Dehydration
DME
Water-gas shift reactionHydrogen
Methane
Hydrocarbons
Methanation
Single-step synthesis
Fischer-Tropsch synthesis
Cu/ZnO/Al2O3
Catalyst:
• Methanol synthesis • Single- and two-step-synthesis of DME
Technological background (I)
Synthesis of (bio)fuels from various resources via synthesis gas (CO/H2)
B. Niethammer, S. Wodarz, M. Betz, P. Haltenort, D. Oestreich, K. Hackbarth, U. Arnold, T. Otto, J. Sauer, “Alternative liquid fuels from renewable resources”, Chem. Ing. Tech. 2018, 90, 99-112.
Institute of Catalysis Research and Technology (IKFT) 6 19.04.2018
Methanol
Isobutylene
Transesterification with fatty acid esters
Methanol-To-Gasoline (MTG) processes
Dehydration
Oxidation + Oligomerization
Methyl tert-butyl ether (MTBE)
Oxymethylene ethers (OME)
Fatty acid methyl esters (FAME)
Gasoline
Dimethyl ether (DME)
Technological background (II)
Synthesis of fuels and fuel additives from (bio)methanol
F. Asinger, Methanol – Chemie- und Energierohstoff, Springer, Berlin, 1986.
Institute of Catalysis Research and Technology (IKFT) 7 19.04.2018
Why OME fuels?
Molecular structure of OMEs: Elimination of soot-NOx trade-off:
• Absence of carbon-carbon bonds => soot-free combustion
• Non-toxic, non-corrosive => safe handling
• Properties similar to diesel => good miscibility with diesel
M. Härtl, K. Gaukel, D. Pélerin, G. Wachtmeister, E. Jacob, “Oxymethylenether als potenziell CO2-neutraler Kraftstoff für saubere Dieselmotoren Teil 1: Motorenuntersuchungen“, MTZ Motortech. Z. 2017, 78(2), 52-59.
OOn
n = 1-5
Institute of Catalysis Research and Technology (IKFT) 8 19.04.2018
Molecular structure & fuel performance (I)
Variation of aldehyde Acetaldehyde + methanol: 1,1-Dimethoxyethane: No detailed fuel investigations Acetaldehyde + ethanol: 1,1-Diethoxyethane: • Diesel: Soot reduction only • Efficient octane enhancer
C O
H
C
H
OC
H
H H
C
C O
H
C
H
OC
H
H H
C
H
H
HH C
H
H
HH
H
C HH
H
HH
Variation of aldehyde (formaldehyde → acetaldehyde) Variation of end group (methyl, ethyl, acetate) Variation of chain length
H
C O
H
C H
H
OC
H
H
H
Hn
• F. Frusteri, L. Spadaro, C. Beatrice, C. Guido, “Oxygenated additives production for diesel engine emission improvement“, Chem. Eng. J. 2007, 134, 239-245. • M.-Z. Vagabov, R. Vagabov, Z. Mangueva, F. Latypova, E. Rakhmankulov, “Use of 1,1-diethoxyethane for increasing knocking resistance of automotive
gasoline“, WO 2012/143465 A1, 2012.
Institute of Catalysis Research and Technology (IKFT) 9 19.04.2018
Molecular structure & fuel performance (II)
H
C O
H
C
H
OC
H
H Hn
H
C O
H
C
H
OC
H
H Hn
C
H
H
HH C
H
H
HH
H
C O COC
Hn
C
H
H
HH C
H
H
OO
Variation of end group
Trioxane + methylal Trioxane + ethylal Trioxane + acetanhydride
0 1 2 3 4 50
20
40
60
80
100
120
140
160
180
Oxymethylene dimethyl ethers Oxymethylene diethyl ethers Oxymethylene diacetates
Cet
ane
num
ber
n, (CH2O units)
• L. Lautenschütz, “Neue Erkenntnisse in der Syntheseoptimierung oligomerer Oxymethylendimethylether aus Dimethoxymethan und Trioxan“, Dissertation, University of Heidelberg, 2015.
• L. Lautenschütz, D. Oestreich, P. Seidenspinner, U. Arnold, E. Dinjus, J. Sauer, “Physico-chemical properties and fuel characteristics of oxymethylene dialkyl ethers”, Fuel 2016, 173, 129-137.
Institute of Catalysis Research and Technology (IKFT) 10 19.04.2018
Molecular structure & fuel performance (III) Variation of chain length b.p. (°C) D20°C (kgm−3) CN
OME0 Dimethylether (DME)
−24 735 (−25 °C) 55
OME1 Dimethoxymethane (DMM) Methylal
42 859 28
OME2 105 977 68
OME3 156 1030 72
OME4 202 1074 84
OME5 242 1106 93
OME>5 waxy not determined
H
C OOC
H
H H
OCO
H
H
H
C
H
H
HC
H
H
H
C OOC
H
H H
OCO
H
H
H
C
H
H
H
H
C
H
C O
H
H
H
C OOC
H
H H
OCO
H
H
H
C
H
H
H
C
H
C O
H
H
HO C
H
H
H
H
H
C
H
H
H
H
H
H
H
H
H C
H
H
H
H
H
H
H
H
H
H
H
H
CH
H
C
H H
HC
H
OC C
O C O C
H
H
O C O C O C
O O C
H
OCOCOCOCO
H H H H H
HHHHn
Institute of Catalysis Research and Technology (IKFT) 11 19.04.2018
4 5 6 7 8 9 10 11 12 13 1420
30
40
50
60
70
80
90
100
20
30
40
50
60
70
80
90
100OME5
OME4
OME3OME2
Cet
ane
num
ber
Chain length, n(C) + n(O)
OMEn
n-hydrocarbon
OME1
n-pentane
n-heptane
n-nonane
n-undecanen-tridecane
Standard diesel (EN 590): > 51
OOn
nOMEn = 1-5
Fuel properties are in good accordance with diesel standards
Cetane numbers of OMEs
D. Deutsch, D. Oestreich, L. Lautenschütz, P. Haltenort, U. Arnold, J. Sauer, “High Purity Oligomeric Oxymethylene Ethers as Diesel Fuels”, Chem. Ing. Tech. 2017, 89(4), 486-489.
Institute of Catalysis Research and Technology (IKFT) 12 19.04.2018
Anhydrous pathways Aqueous pathways
• Reactions starting from DMM • Reactions starting from methanol • High OME selectivity • Low-cost starting materials • Low amounts of byproducts • Formation of byproducts (hemiacetals) • Comparatively simple product separation • Removal of water • Costly starting materials
OME synthesis: State of the art
Methanol
Trioxane
Dimethoxymethane
O O
FormaldehydeO
O O
DMM
OMEn
OOn
OMEn
OOn
DME ODimethyl ether
1 2
3
L. Lautenschütz, D. Oestreich, P. Haltenort, U. Arnold, E. Dinjus, J. Sauer, “Efficient synthesis of oxymethylene dimethyl ethers (OME) from dimethoxymethane and trioxane over zeolites”, Fuel Process. Technol. 2017, 165, 27-33.
Institute of Catalysis Research and Technology (IKFT) 13 19.04.2018
OME synthesis: DMM + trioxane
Reaction conditions:19 g DMM, 7.5 g trioxane, 0.075 g Amberlyst 36, T = 60 °C
Recent progress:
• Zeolite BEA catalyst • Reaction within minutes at 25 °C • Reliable separation of catalyst • Elimination of byproducts
OME3-5 yield: ∼30 wt%
O On
O O Acidic catalyst+
O
O O1
Institute of Catalysis Research and Technology (IKFT) 14 19.04.2018
Reaction conditions: 40 g MeOH, 60 g formaldehyde (5% water), 1.0 g Amberlyst 36, T = 80 °C
OME synthesis: Methanol + formaldehyde
O OnH
OH
On
Acidic catalyst+H3C-OH + H2O2
Recent progress:
• Highly active Dowex catalysts • High catalyst stability • Equilibria and kinetics determined • Continuous production demonstrated
OME3-5 yield: ∼12 wt%
Institute of Catalysis Research and Technology (IKFT) 15 19.04.2018
• Continuous long-term operation • Variable temperatures and pressures • Defined feed compositions • Recording of concentration profiles • Recording of temperature profiles • Analysis via online-GC/MS • Catalyst long-term testing • Kinetic modelling
0 1 2 3 4 17 180,00
0,05
0,10
0,15
OME_1 OME_2 OME_3 OME_4 OME_5
Mas
s fr
actio
n / g
g-1
Time / d
D. Oestreich, L. Lautenschütz, U. Arnold, J. Sauer, “Reaction kinetics and equilibrium parameters for the production of oxymethylene dimethyl ethers (OMEs) from methanol and formaldehyde”, Chem. Eng. Sci. 2017, 163, 92-104.
OMEs from methanol + formaldehyde Continuously operating laboratory plant
Run at 90% of maximum methanol conversion Reaction conditions: p-FA/MeOH = 3:2 g/g, T = 40 °C, p = 0.1 MPa, Dowex50Wx2 (200-400 mesh)
2
Institute of Catalysis Research and Technology (IKFT) 16 19.04.2018
Diesel + OMEs Water OMEs Hemiacetals Trioxane Formaldehyde Methanol FA
MeOH
Wate
r
Trioxa
ne
OME-1
OME-2
OME-3
OME-4
OME-5
OME-5+
OME-OH-1
OME-OH-2
OME-OH-3
0.00
0.05
0.10
0.15
Mas
s fr
actio
n / g
g-1
Diesel phase Aqueous phase
• U. Arnold, L. Lautenschütz, D. Oestreich, J. Sauer, EP 2 987 781 A1, 2016. • D. Oestreich, L. Lautenschütz, U. Arnold, J. Sauer, “Production of oxymethylene dimethyl ether (OME)-hydrocarbon fuel blends
in a one-step synthesis/extraction procedure”, Fuel 2018, 214, 39-44.
OMEs from methanol + formaldehyde Reaction & Extraction
2a
Institute of Catalysis Research and Technology (IKFT) 17 19.04.2018
OME synthesis: DME + trioxane
O On
O Acidic catalystAcidic catalyst+
O
O O3
0 20 40 600.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8 TRI
mas
s fra
ctio
n ed
ucts
/ g/
g
time / h
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
OME-1 OME-2 OME-3 OME-4 OME-5
mas
s fra
ctio
n pr
oduc
ts /
g/g
Reaction conditions: ntrioxane/nDME = 0.25, 0.4 wt% H-BEA 25, 80 °C
Recent progress:
• H-BEA25 catalyst • Mild reaction conditions (80 °C) • Low reaction rate • Kinetic control of selectivity possible
OME3-5 yield: ∼20 wt% (Liquid product phase, 16 h)
Institute of Catalysis Research and Technology (IKFT) 18 19.04.2018
1 2 3 4 50
5
10
15
20
25
30
35
40
16 h 24 h 48 h 72 h
OM
E fra
ctio
n (w
t%)
OMEn
Reaction time
1 2 3 4 50
5
10
15
20
25
30
35
40
16 h 24 h 48 h
OM
E fra
ctio
n (w
t%)
OMEn
Reaction time
1 2 3 4 50
5
10
15
20
25
30
35
40
16 h 24 h
OM
E fra
ctio
n (w
t%)
OMEn
Reaction time
1 2 3 4 50
5
10
15
20
25
30
35
40
16 h
OM
E fra
ctio
n (w
t%)
OMEn
Reaction time
80 °C, 18 bar, ntrioxane/nDME = 0.25, 0.4 wt% catalyst
• P. Haltenort, K. Hackbarth, D. Oestreich, L. Lautenschütz, U. Arnold, J. Sauer, “Heterogeneously catalyzed synthesis of oxymethylene dimethyl ethers (OME) from dimethyl ether and trioxane”, Catal. Commun. 2018, 109, 80-84.
• T.J. Goncalves, U. Arnold, P.N. Plessow, F. Studt, “Theoretical Investigation of the Acid Catalyzed Formation of Oxymethylene Dimethyl Ethers from Trioxane and Dimethoxymethane”, ACS Catal. 2017, 7, 3615-3621.
Mass fractions of OME1-5 vs. time
Direct insertion of trioxane into DME
Formation of OMEn mixtures in secondary reactions (transacetalization)
OO
OO+ O O O O
OOx
OOy
+ OOx-1
OOy+1
+
• Efficient OME synthesis from DME with zeolite H-BEA as catalyst • Accordance with other experimental and theoretical findings for DMM + trioxane
OME synthesis: DME + trioxane 3
Institute of Catalysis Research and Technology (IKFT) 19 19.04.2018
FA DMM Trioxane DMM + Trioxane Distillation Recycling
FA DME Trioxane DME + Trioxane Distillation Recycling
FA DMM DMM + FA Distillation Recycling Water removal
FA MeOH + FA Distillation Recycling Water removal
FA MeOH + FA Extraction Recycling
■ Synthesis of educts; ■ OME forming reaction; ■ Work-up
FA = formaldehyde, DMM = dimethoxymethane
Main process steps starting from methanol
Comparison of OME production processes
3
2
1
2a
Institute of Catalysis Research and Technology (IKFT) 20 19.04.2018
OME synthesis • Optimization of OME synthesis from DME • Theoretical investigations on catalysts for OME synthesis
Fuel applications • Combination of OMEs with other fuels • Investigations on (storage) stability
Chemical modification of OMEs • Variation of end groups • Modification for non-fuel applications
Life cycle assessment with updated technological data • In the Power-to-X context • Entire process chain starting from renewable resources
(e.g. woody biomass)
Current work
Institute of Catalysis Research and Technology (IKFT) 21 19.04.2018
Synthesis of OMEs from renewables via “Green Methanol“
Synthesis gas
(CO + H2)
Biomass, residues
Methanol
Coal, natural gas
CO2 + H2
Challenges
• X. Zhang, A.O. Oyedun, A. Kumar, D. Oestreich, U. Arnold, J. Sauer, “An optimized process design for oxymethylene ether production from woody-biomass-derived syngas”, Biomass Bioenergy 2016, 90, 7-14.
• N. Mahbub, A.O. Oyedun, A. Kumar, D. Oestreich, U. Arnold, J. Sauer, “A life cycle assessment of oxymethylene ether synthesis from biomass-derived syngas as a diesel additive”, J. Cleaner Prod. 2017, 165, 1249-1262.
Institute of Catalysis Research and Technology (IKFT) 22 19.04.2018
• Soot + NOx + CO2 reduction possible
• Comprehensive data on high-purity OMEs are available yet
• OME synthesis from DMM and trioxane is highly developed
• Recent progress in OME synthesis from methanol or DME
• Data for process design available to a large extent
• Up-scaling feasible in the near future
• There is still a large potential for optimization
- Separation of OMEs - Recycling of byproducts - Removal of water
Summary & Outlook
Institute of Catalysis Research and Technology (IKFT) 23 19.04.2018
Fachagentur Nachwachsende Rohstoffe / BMEL Joint research project (FKZ 22403814): Oxymethylene ethers (OME): Eco-friendly diesel additives from renewables
Acknowledgements
P. Haltenort K. Hackbarth D. Oestreich L. Lautenschütz J. Sauer D. Deutsch S. Silbernagel-Donath