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Separation Enhanced Dimethyl Ether (DME) SynthesisDr. Ir. Jurriaan Boon

21 June 2017, Eurogress, Aachen

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R&D Strategy ECN Energy & Industry Programme

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Separation enhanced DME synthesis

• DME: promising fuel for compression ignition vehicles

• Production of DME from biomass

• Conventional production of DME

• Separation enhanced DME synthesis

• Fledged: DME from biomass, renewable electricity

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Dimethyl ether (DME)

C2H6O

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DME: Fuel of choice

Volvo Sustainability report 2013

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DME: Fuel of choice

• Promising in terms of GHG emissions, efficiency, economy

• Can be handled like LPG

• Behaves like diesel in a compression ignition enginewithout soot formation!

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DME - The next big thing

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Fledged: DME from biomass and hydrogen

2016-2020

GasifierDME

synthesis

Electrolyser

DMESyngas with adjusted composition (M<2)

Biomass

H2

O2

Combustor

Biomass (if needed)

Flue gas to stackair

steam

water

Target syngas composition (M=2)

Circulating solids

𝑀 =H2 − CO2CO + CO2

= 2

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Production of DME

Methanol synthesisCO2+3H2⇌CH3OH+H2O

Water-gas shift (WGS)CO+H2O⇌H2+CO2

Methanol dehydration

2CH3OH⇌CH3OCH3+H2O

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Conventional production of DME

Methanol synthesis

Methanol separation

Synthesis gas

H2/CO/CO2 recycle

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Conventional production of DME

Methanol synthesis

Methanol separation

DME synthesis DME separation DMESynthesis

gas

H2/CO/CO2 recycle Methanol recycle

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Production of DME from biomass

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Conventional versus direct synthesis

Methanol synthesis

Methanol separation

DME synthesis DME separation DMESynthesis

gas

a) Conventional DME productionH2/CO/CO2 recycle Methanol recycle

Direct DME synthesis DME separation DME

b) Direct DME productionCO/CO2 recycle

SEDMES DME separation DME

c) Sorption-enhanced DME production (SEDMES)Optional CO recycle

Synthesis gas

Synthesis gas

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Steam separation enhanced DME synthesis

Methanol synthesisCO2+3H2⇌CH3OH+H2O

Water-gas shift (WGS)CO+H2O⇌H2+CO2

Methanol dehydration

2CH3OH⇌CH3OCH3+H2O

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Thermodynamic equilibrium

0

5

10

15

20

25

30

150 200 250 300 350

CO

, CO

2, D

ME,

CH

3O

H /

mo

l%

Temperature / °C

DME

CH3OH

CO

CO2

Composition 3

25 bar(a)

54 mol% H2

15 mol% CO7.7 mol% CO2

𝑀 =H2 − CO2CO + CO2

= 2

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Equilibrium with in situ water removal

275 °C25 bar(a)

54 mol% H2

15 mol% CO7.7 mol% CO2

0

5

10

15

20

25

30

35

40

0.001 0.01 0.1 1

Co

mp

osi

tio

n /

mo

l%

Steam slip / mol%

DME

CH3OH

CO

CO2

Composition 3

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Experimental: sorption enhanced DME synthesis

Cu/ZnO/Al2O3 catalystZeolite 3A

syngas

effluent

275 °C25 bar(a)

400 °C2 bar(a)

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Experimental: sorption enhanced DME synthesis

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Experimental: breakthrough test

0

5E-11

1E-10

1.5E-10

2E-10

2.5E-10

3E-10

3.5E-10

4E-10

4.5E-10

0

2

4

6

8

10

12

14

16

0 20 40 60

MS

sign

al /

A

ND

IR c

on

cen

trat

ion

/ m

ol%

Time / min

CO (NDIR)

CO2 (NDIR)

DME (MS)

CH3OH (MS)

H2 (MS)

H2O (MS)

Composition 3 275 °C25 bar(a)

54 mol% H2

15 mol% CO7.7 mol% CO2

Proof of concept

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Separation enhanced DME synthesis

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Pro

du

ct C

-dis

trib

uti

on

[mo

l%]

MethOH

CO

CO2

DME

Conventional direct DME(thermodynamic calculation)

Sorption enhanced DME(experimental observation)

275°C, 25 bar

Product

Feed

Sorption-enhanced DME synthesis Increased CO/CO2 flexibility Increased DME yield Decreased CO2 content𝑀 = 2

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Conventional, direct, sorption-enhanced synthesis

Methanol synthesis

Methanol separation

DME synthesis DME separation DMESynthesis

gas

a) Conventional DME productionH2/CO/CO2 recycle Methanol recycle

Direct DME synthesis DME separation DME

b) Direct DME productionCO/CO2 recycle

SEDMES DME separation DME

c) Sorption-enhanced DME production (SEDMES)Optional CO recycle

Synthesis gas

Synthesis gas

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Production of DME from biomass

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Production of DME from biomass

Sorption-enhanced gasification Sorption-enhanced DME synthesis

The FLEDGED project will deliver a process for bio-based dimethyl ether (DME) production from biomass gasification, validated in industrially relevant environment (TRL5).

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Separation enhanced DME synthesis

• DME: promising fuel for compression ignition vehicles• Production of DME from biomass• Conventional production of DME

– Low DME yield– CO2 production– Complex separation

• Sorption enhanced DME synthesis– Increased CO/CO2 flexibility– Increased DME yield– Decreased CO2 content

• Fledged: DME from biomass, renewable electricity

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http://www.fledged.eu/@FledgedProject

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http://www.ecn.nl/research-programme/energy-and-industry/@ECN

Gas separation, treatment & conversion• Development of sorption technology to reduce industrial CO2 emissions• Development of membrane reactors for hydrogen production• Conversion of industrial waste streams into chemicals and transport fuels

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http://www.ecn.nl/research-programme/energy-and-industry/@ECN

Industrial integration of renewable electricity• Development of processes to produce chemicals and fuels

with the help of electricity, e.g. hydrogen• Development of technology to flexibly convert

renewable electricity into heat

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This project has received funding from the ministry of Economic Affairs of The Netherlands through the ECN Ideation Challenge programme. This project has also received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 727600.