1

Overview of Topsøe Synthesis Technologies for BTL and bio-SNG

Thoa Nguyen and Finn JoensenHaldor Topsøe A/S

Introduction to Haldor Topsøe

2

OutlineHaldor Topsøe – Brief intro

The TIGAS technology– The liquid fuel scenario

– The TIGAS process

– Process Demonstration

SNG catalysts and technology– Process

– References

– Impurities

– CAPEX example

Company factsEstablished 1940

Ownership: Haldor Topsøe Holding A/S (100%)

Headquarters in Lyngby, Denmark

Annual turnover (2011): ~587 MM EUR(>4.4 billion DKK)

Number of employees ~2100 (R&D >300)

3

Synergies - the Topsøe way

Founded on the belief that we build and retain a position as second to none in catalysis through applied fundamental research.

This notion still governs the company’s business activities.

R&D Engineering

Processdesign

Catalystproduction

Sales&

Support

Catalyst supplyCatalysts developed in-house

Catalysts manufactured in own facilities– Frederikssund, Denmark

– Houston, Texas

Frederikssund

Houston

4

Scope of supplyProcess licenses

Catalysts

Engineering services– Basic engineering– Detailed engineering– Purchasing

Site supervision– Erection– Start-up & test run

Equipment supply

Training of operators

Process simulators

Technologies and business areasAmmonia technology– Fertilizer industry

Hydrogen and Hydroprocessing technology– Refining industry

Environmental technology, WSA, DeNOx and SNOX– Environmental and power industries

Synthesis gas / methanol / DME / SNG / gas to liquid technologies– Petrochemical industries, (methanol)

– Energy and environmental industries

5

From Syngas to Synfuels -The TIGAS Process

The Fuel Challenge:- Meeting the Ever-Increasing Demand for Fuel

Green

6

Peak Oil

1972: Oil will run out within 30 years ……………………………..2012: Oil will run out within 30 years

World Oil Reserves

Still more difficult to access/processHigher production costsIncreasing demand Higher fuel pricesSynfuels become attractive

CoalNatural GasBiomassWaste

7

Methanol Gasoline, Basic Equations

2H2 + CO = CH3OH

CH3OH = CH2 + H2O

1 t MeOH 0.4725 t ”CH2” (14/32)

Approx. 0.4 t gasoline ; 0.05 t LPG

Typical Product Distribution

Cn

8

Gasoline

C3-C4

Water

MTGMethanol To Gasoline

Synthesis Gas

TIGASTopsøe Integrated Gasoline Synthesis

Simple process layout No methanol condensation / re-evaporation

Moderate pressureSimple – Selective – Efficient – Flexible

MeOH/DME Methanol

DME Gasoline

Low recycle rates

Combined MeOH/DME Synthesis

H (kJ/mol)

2H2 + CO = CH3OH 90.7

2CH3OH = CH3OCH3 + H2O 23.6

CO + H2O = CO2 + H2 41.1

3H2 + 3CO = CH3OCH3 + CO2

9

Con

vers

ion

(H2+

CO

)

Pressure (bar g)

T = 250 C

Feed Gas (mol%):

H2 = 51

CO = 48

CO2 = 1

0

20

40

60

80

100

0 20 40 60 80 100

MeOH

MeOH / DME

Syngas Eq. Conversion vs. Pressure

TIGASTopsøe Improved Gasoline Synthesis

0

20

40

60

80

100

0 20 40 60 80 100

MeOH

MeOH / DME

10

Topsoe Demonstration Plant, 9000 hrs

T/d & kg/hPilots

Historical Perspective

H-ZSM-5

11

(Waste) Wood to Gasoline

Demonstration Project

Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes

Wood to Gasoline Demonstration Project

OXYGEN

Green Gasoline From Wood Using Carbona Gasification and Topsoe TIGAS Processes

BIOMASS

ASH

GASIFIERTAR REFORMER

BIOMASS

ASH

GASIFIERTAR REFORMER

TAR R

EFOR

MER

BIOMASS

GA

SIFIER

ASH

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

GasCleaning Gasoline MeOH/DME

12

Pilot Plant Studies

Impact of Process ConditionsProduct DistributionRON/MON DataKinetic ModelingAgeing StudiesGasoline post-treatment

– Durene isomerization– Octane boosting Pseudo-Adiabatic Pilot (DK)

13

Reaction Mechanism

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

GSK-10 Kinetic Model

LPGOIONOPOAO

OOxy

k

k

k

k

k

k

6

5

4

3

2

1

0 20 40 60 800

0.01

0.02

0.03

0.04

0.05

Data Point

Tota

l Wei

ght F

ract

ion

of L

ump

O

Oxygenates

MeasuredCalculated

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Fit of T-Profiles from PilotC

onve

rsio

n (H

2+C

O)

Pressure (bar g)

T = 250 C

Feed Gas (mol%):

H2 = 51

CO = 48

CO2 = 1

0

20

40

60

80

100

0 20 40 60 80 100

MeOH

MeOH / DME

40 % N2

0

20

40

60

80

100

0 20 40 60 80 100

MeOH

MeOH / DME

Syngas Eq. Conversion vs. Pressure

Enabling Air-Blown Gasification

15

Skive District Heating/Power Plant

16 MWth

~ 100 bbl/d

2 atm (Air)

7 MWth

16 MWthN2

Gedankenexperiment

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Gedankenexperiment…

20,600 inhabitants

6000 households

6000 pass. cars

30 km/d

11.3 km/l

15,900 l Gasoline/d

~ 100 bbl/d

Thank you for your attention !

Any questions ?

Gosh I’m hungry

www.topsoe.com

The prospects of steadily increasing oil prices, increasing global demand for automotive fuels coupled with environmental and energy security concerns make synfuels part of the equation to secure future energy supply.

In this context the TIGAS technology offers versatile, selective and efficient routes for the conversion of syngas to produce a clean gasoline product directly adaptable to existing fuel infrastructure.

Conclusions

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SNG catalysts and technology

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Topsøe technologies for coal conversion

Airseparation

unit

Airseparation

unit

GasificationGasification Sour ShiftSour ShiftAcid gas

removal

Acid gas

removal

Sulphur recovery (WSA)

Sulphur recovery (WSA)

Synthesis(TREMPTM)Synthesis

(TREMPTM)

O2

SteamCO2

Sour gas

WetSulphuric Acid(instead of Klaus)

Air

CoalPolishingPolishing

HTAS licenses:MethanolDMEAmmoniaSNGHydrogenTIGAS

Substitute Natural Gas (SNG)What it is:

Essentially methane generated from syngas methanation.

Raw materials:

Syngas generated from gasification of biomass, waste, coal, petcoke

Markets:

- Where NG resources limited or non-existing

- Where biomass, waste, coal and/or petcoke abundant

- Strategic energy sourcing (independence, security)

- To NG pipeline, LNG or as fuel gas

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Mole%

CH4 94 - 98

CO2 0.2 – 3

H2 0.1 – 2

CO <100 ppm

N2 + Ar 1 - 3

HHV, KJ/Nm3 37,000 - 40,000

Typical specification for SNG

SNG fundamentals and references

Methanation to SNG

+200 references in steam reforming, using Nickel-based catalysts (front-end ammonia, hydrogen, methanol, other)

More than 50 years of Topsøe experience

Sintering stability

Methanation activity

Carbon formation (whisker, gum)

CO + 3H2 CH4 + H2O (+206 kJ/mol)CO2 + 4H2 CH4 + 2H2O (+165 kJ/mol)

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Signature features of methanation via TREMP

HPboiler

Feed

Super-heater

Water

SNG

GasCooler

CoolingTrain

HPboiler

High exit temperature (700 °C)

Haldor Topsøe TREMP processEqulibrium curve

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

0 10 20 30 40 50 60 70 80 90 100

% CH4, dry

T, °

C

Operating window +100 C

Recycle reduced 50%

Lower investment

Lower operational cost

HP steam

Product spec

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Large temperature increase in 1st reactor benefits recycle cost

Inlet T (°C)

Exit T(°C)

Recycle work

(relative)

Compressor CAPEX(relative)

Base Case 260 700 1 1

Effect of lower exit-temperature

Case 1 260 625 1.6 1.3

Case 2 260 450 4 2.3

Effect of higher inlet-temperature

Case 3 330 700 1.2 1.1

Case 4 330 625 1.8 1.4

Case 5 330 450 5.8 2.9

For TREMP compressor cost is 20% of total investment

SNG referencesPlant Client Capacity Nm3/d YearADAM1 / IRMA NFE, Jülich, Germany 4.800 1979-1985

ADAM2 demonstration NFE, Jülich, Germany 48.000 1980-1983

Selected for:SRC2 Stearns Roger, US 1.7 mio 1977-81

(Cancelled ’81)

Power Holding Power Holding,Illinois, US 4.3 mio 2006

Cline Group Illinois Basin, US ~ 3.4 mio 2008

Lake Charles Lake Charles Cogen. 2008

Non-disclosed Illinois, US ~2.4 mio 2006

Engineering studies:2 clients US Non-disclosed Ca. 5 mio. 2006/2008

Projects:Gobigas (Bio-based) Gothenburg, Sweden 0.24 mio. 2007

Undisclosed Illinois, US 2009

Qinghua China 4 mio 2009

Undisclosed (Bio-based) Sweden 2010

POSCO South Korea 2,25 mio 2010

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Unit Product flow, Nm3/hr (MSCFH)

P, bar (psig)

Operation, hours

ADAM I 200 (7.5) 28 (406) 2300

ADAM II 3000 (112) 47 (682) 6000

IRMA (Isoterm) 200 (7.5) 28 (406) 1400

Small Pilots 15 (0.6) 30 (435) >25000

Topsoe Pilot 12 (0.45) 30 (435) >20000

More than 55000 demonstration hours

Operating experience with MCR-2X

Catalyst experienceADAM 1

ADAM 2

Totally more than 50000 hours of operation in demo

plants and pilots

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High temperature methanation catalyst (MCR)Slight modifications have given an even more stable catalyst

~1980

300

400

500

600

700

0 50 100

Distance from inlet (cm)

Tem

pera

ture

(ºC

)1 h358 h1028 h

2010

Results from Jülich / Wesseling demonstation

Reactor designs– Isothermal reactors

SaltBoiling water

– Adiabatic reactors– Shell cooled– Gas cooled reactors

Catalyst– MCR-2

Demonstrated up to 800 deg. CMore shapes

– MCR-4

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Low-temperature methanation (PK-7R)Used in all Ammonia plants– CO and CO2 are a poison for an ammonia catalyst

Used in some of the old H2 plants– CO and CO2 are a poison for some hydro treating catalysts

Haldor Topsøe has ~150 references worldwide

Requirement to the feed gas composition

00.32

624222

6242222

HCHCOCOCOHCHCOCOHM F

00.32

22

COCOCOHM E

Module equations for entrained flow and fixed bed gasifiers

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Example: Feed gas 30 barg, Methane 0%, 0,75% inerts

Feed gas variation harm product quality

Module 2.90 2.95 3.00 3.05 3.10

H2 74.01 74.33 74.60 74.95 75.24

CO 24.44 24.12 23.85 23.50 23.21

CO2 0.80 0.80 0.80 0.80 0.80

CH4 92.4 93.1 93.4 92.3 88.5

H2 2.1 2.5 3.1 5.1 9.0

CO2 2.83 1.75 0.88 0.08 0.00

HHV 37.0 37.3 37.5 37.3 36.3

Wobbe 48.4 49.4 50.1 50.7 50.2

Feed into methanation plant

Dry SNG product

00.32

22

COCOCOHM EModule

Requirement to the feed gas impuritiesExamples for poisons for methanation catalyst

Chlorine

Arsenic

Oxygen

Sulphur– COS

– H2S

– CS2

– C4H4S

– CH4S

26

CAPEX estimateTotal capacity: 1,400,000,000 Nm3/a

Total price: approximately 1.5 billion EUR(install cost, all inclusive)

– Syngas generation etc. 65%

– Rectisol 15%

– TREMP 10%

– Sour shift 5%

– SRU 5%

– Total 100%

Summary of TREMP benefitsHigh capacity:

– Train size above 200,000 Nm3/h

Max. value of released energy: – 85% high-pressure steam (540°C, 140 bar)

140 bar g @ 540°CUp to 3.8 kg / Nm3 of SNG

Minimum recycle flow– Reduced CAPEX, OPEX (small compressor, heat exchangers electricity)

Possible elimination of recycle compressor for methane-containing feed gas (once-through).

– Reduced CAPEX and OPEX, very high reliability

High Quality: In-process compensation for feed-gas module variation– Combining high performance with robust process

No continuous emissions to the atmosphere.Clean Process Condensate (can be used as make-up for the steam system)