refuels – raw materials, processes and applications for ......synthesis of fuels and fuel...

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


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


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


- 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.


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.


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


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.


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.


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


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.


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.


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


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%


• 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


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


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)


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


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


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


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.


• 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


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

refuels – raw materials, processes and applications for ......synthesis of fuels and fuel...

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