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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
14
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
16
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
17
SNG catalysts and technology
18
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
19
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)
20
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
21
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
22
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
23
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
24
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
25
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)