Methanol to gasoline(MTG) as a green pathto synthetic fuelsThoa Nguyen, PhD.

Project manager, Chemicals R&D, Haldor Topsøe A/S

10 May 2017

2

Outline

• Wood to gasoline demonstration project• The process• The chemistry• Other alternatives to green fuels• Conclusions

3

Wood-to-Gasoline Demonstration20-25 bbl/d, Des Plaines, IL, 2010-2014

DOE Award No. DE-EE0002874

Biofuel

4

The green gasoline project

• DOE grant: 25 mio. USD• Project team cost share: 10 mio. USD• 2010: preliminary design• 2011: start of procurement• 2012: shakedown tests• 2013: gasoline tests

5

The green gasoline project

• 20- 25 bpd gasoline• 1.3 bbl gasoline and 0.2 bbl LPG per dry ton wood• Wood pellets as feed

6

Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes

OXYGEN

BIOMASS

ASH

GASIFIERTAR REFORMER

BIOMASS

ASH

GASIFIERTAR REFORMER

TAR

REFO

RM

ER

BIOMASS

GASIFIER

ASH

http://www.energy.gov/news2009/releases.htm

GasCleaning

OXYGEN

Entire value chain: biomass in à gasoline out

Biogasoline Demonstration Plant

MeOH/DME Gasoline

7

Process Flow Diagram GasolinereactorMeOH Gasoline

8

T/d & kg/hPilots

H-ZSM-5

Historical Perspective

9

Current MTG Test Facility (Denmark)

8 bpd demonstration facility (Houston, TX)

lb/h Test Facility(Denmark)

TIGAS (Topsøe Improved Gasoline Synthesis)

0.6 bpd pilot facility (Ravnholm, DK)

10

• Gasification & Tarreforming (existing)

• Morphysorb® AGR unit(existing)

• Utility units & controlsystem (existing)

• Syngas compression (new)• TIGAS synthesis unit (new)• Gasoline & waste water

tanks (new)

Biofuel facility

11

Construction: Zeton workshop

12

Transportation: reactor and reactor container

13

Construction: lifting

14

Construction: roof removal to install the TIGAS container in

15

Shakedown test

• Stepwise full-scale operation of each major section at process conditions:• Gasification section (Nov 2012)• Gasification + AGR sections (Dec 2012)• Gasification + AGR + TIGAS (Jan 2013)

• Final commissioning of feedstock delivery system• CO2 supply and purge system, syngas compressor, AGR upgrades, and TIGAS plant operation

• First gasoline production (100 gal)

16

Aromatics in gasoline

Hours on stream (full value chain)

Gasoline octaneGasoline reactor temperature profile

Hours on stream (full value chain)Relative bed height

Nor

mal

ized

axia

ltem

pera

ture

Vol%

Wood to Gasoline Demonstration Project

17

Complete integrated operation

Limited duration(budget constraints)

MAR 13 OCT/NOV 13 MAR 14

Total gasoline production over period = 9870 gallons

Test #1- #3: summary of results

18

Gasoline testing

• Engine emissions testing at Southwest Research Institute• Tested a 80/20 high biomass TIGAS/gasoline blend.• Emission levels better than for conventional gasoline.• Found to be ”substantially similar” to conventional gasoline

• Fleet test• Testing 8 vehicles (EPA Standard Road Cycle)

• 2 Camry (2.5 L PFI),• 2 Corolla (1.8 L PFI)• 2 F-150 (3.5 L V6 EcoBoost®),• 2 Fusion (1.5 L EcoBoost®)

• Commercial gasoline vs. 50% biogasoline blend• Accumulate 75,000 miles per vehicle• Engine inspections• Engine emission tests @ 4000 & 75,000 miles

19 Pseudo-Adiabatic Pilot, Ravnholm

• 290-430°C• 15-20 barg• WHSV = 0.8 – 2.6 h-1 fixed bed• Gasoline reactor: ZSM-5• Cycle length: 10-40 days• Lifetime: 1-2 years

Methanol to gasoline (MTG) GasolinereactorMeOH Gasoline

20

MeOH/DME C3H6 (CnH2n) + H2O

C3H6 (CnH2n) + MeOH/DME

CnH2n

CnH2n

CnH2n+2CnH2n+2

CnH2n+2

CnH2n

HC-Pool

Homologation

Dehydrocyclization

MeOH(DME)

+ H2O

+ H2O

Reaction Mechanism

21

Cn

Typical TIGAS Product Distribution

P I O N

A

22

• Address cold flow properties

• Synthetic gasoline from H-ZSM-5 containsdurene

• Durene freezes at 79.2ºC

• Improve cold flow properties by isomerization

• Octane rating

• In the treatment to reduce durene, octane lossif aromatics are saturated

• Synthetic gasoline is also rich inpseudocumene and one of its isomers hasexcellent octane rating

• Boosting octane by isomerization

Two-fold process objectivesGasoline Upgrading Unit (GUU)

23

Other fuel routes

MeOH Gasoline

MeOH/DME Gasoline

GUU

GUU

Methanol togasoline (MTG)

Syngas togasoline (STG)

CH4, WGS, CH3OH, DME, MTH, NH3

24

Summary• MTG: direct conversion of methanol to gasoline• Topsøe MTG: TIGAS is a versatile technology for conversion of syngas to gasoline• Economy

• Feasible without subsidy at previously high oil prices

• Co-production of power and fuel• Feasible solution to counteract imbalances• Improves overall system flexibility• Maximizes operator revenue• Simplicity and efficiency makes TIGAS suitable for co-generation

25

World largest gasoline plant – TIGAS in Turkmenistan

• 175,000 Nm3/h natural gas• Capacity 1800 ton pr. day (~15,500 BPD) gasoline• To be started up in 2018