Overview of Topsøe Synthesis Technologies for BTL and bio-sng

Transcription

1 Overview of Topsøe Synthesis Technologies for BTL and bio-sng Thoa Nguyen and Finn Joensen Haldor Topsøe A/S Introduction to Haldor Topsøe 1

2 Outline Haldor 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 facts Established 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) 2

3 Synergies - the Topsøe way Process design Founded on the belief that we build and retain a position as second to none in catalysis through applied fundamental Sales research. & R&D Engineering Support This notion still governs the company s business activities. Catalyst production Catalyst supply Catalysts developed in-house Catalysts manufactured in own facilities Frederikssund, Denmark Houston, Texas Frederikssund Houston 3

4 Scope of supply Process 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 areas Ammonia 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 4

5 From Syngas to Synfuels -The TIGAS Process The Fuel Challenge: Gree n - Meeting the Ever-Increasing Demand for Fuel 5

6 1972: Oil will run out within 30 years..2012: Oil will run out within 30 years Peak Oil World Oil Reserves Still more difficult to access/process Higher production costs Increasing demand Higher fuel prices Synfuels become attractive Coal Natural Gas Biomass Waste 6

7 Methanol Gasoline, Basic Equations 2H 2 + CO = CH 3 OH CH 3 OH = CH 2 + H 2 O 1 t MeOH t CH 2 (14/32) Approx. 0.4 t gasoline ; 0.05 t LPG Typical Product Distribution C n 7

8 TIGAS MTG Topsøe Integrated Gasoline Synthesis Methanol To Gasoline Synthesis Gas Methanol MeOH/DME C 3 -C 4 DME Gasoline Gasoline Simple process layout Water No methanol condensation / re-evaporation Simple Selective Efficient Flexible Low recycle rates Moderate pressure Combined MeOH/DME Synthesis H (kj/mol) 2H 2 + CO = CH 3 OH CH 3 OH = CH 3 OCH 3 + H 2 O 23.6 CO + H 2 O = CO 2 + H H 2 + 3CO = CH 3 OCH 3 + CO 2 8

9 Syngas Eq. Conversion vs. Pressure MeOH / DME T = 250 C Feed Gas (mol%): Conversion (H 2 +CO) MeOH H 2 = 51 CO = 48 CO 2 = Pressure (bar g) TIGAS Topsøe Improved Gasoline Synthesis MeOH / DME 60 MeOH

10 Topsoe Demonstration Plant, 9000 hrs Historical Perspective T/d & kg/h Pilots H-ZSM-5 10

11 (Waste) Wood to Gasoline Demonstration Project Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes Wood to Gasoline Demonstration Project Green Gasoline From Wood Using Carbona Gasification and Topsoe TIGAS Processes BIOMASS BIOMASS GASIFIER TAR REFORMER TAR REFORMER GASIFIER Gas MeOH/DME Gasoline Cleaning ASH ASH OXYGEN 11

12 Pilot Plant Studies Impact of Process Conditions Product Distribution RON/MON Data Kinetic Modeling Ageing Studies Gasoline post-treatment Durene isomerization Octane boosting Pseudo-Adiabatic Pilot (DK) 12

13 Reaction Mechanism MeOH/DME HC-Pool C 3 H 6 (C n H 2n ) + H 2 O C 3 H 6 (C n H 2n ) + MeOH/DME Homologation + H 2 O + H 2 O MeOH(DME) C n H 2n+2 C n H 2n Dehydrocyclization C n H 2n C n H 2n C n H 2n+2 C n H 2n+2 GSK-10 Kinetic Model Oxy O O O O O k k1 2 O A k 3 P k 4 N k 5 I k 6 LPG Total Weight Fraction of Lump O Oxygenates Measured Calculated Data Point 13

14 Fit of T-Profiles from Pilot Syngas Eq. Conversion vs. Pressure MeOH / DME MeOH / DME T = 250 C Feed Gas (mol%): Conversion (H 2 +CO) Enabling Air-Blown Gasification MeOH MeOH H 2 = 51 CO = 48 CO 2 = % N Pressure (bar g) 14

15 Skive District Heating/Power Plant 16 MW th Gedankenexperiment 2 atm (Air) N 2 16 MW th 7 MW th ~ 100 bbl/d 15

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 Conclusions The prospects of steadily increasing Thank you for your attention! oil prices, increasing global demand for automotive fuels coupled with environmental and energy security concerns make synfuels part of the Any questions? 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 Gosh I m hungry clean gasoline product directly adaptable to existing fuel infrastructure. 16

17 SNG catalysts and technology 17

18 Topsøe technologies for coal conversion Air Air separation unit O 2 Sulphur recovery (WSA) Sour gas Wet Sulphuric Acid (instead of Klaus) HTAS licenses: Methanol DME Ammonia SNG Hydrogen TIGAS Coal Gasification Sour Shift Acid gas removal Polishing Synthesis (TREMP TM ) CO 2 Steam 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 18

19 Typical specification for SNG Mole% CH CO H CO <100 ppm N 2 + Ar 1-3 HHV, KJ/Nm 3 37,000-40,000 SNG fundamentals and references Methanation to SNG CO + 3H 2 CH 4 + H 2 O CO 2 + 4H 2 CH 4 + 2H 2 O (+206 kj/mol) (+165 kj/mol) +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) 19

20 Signature features of methanation via TREMP Feed Gas Cooler Superheater HP boiler HP boiler Cooling Train SNG Water High exit temperature (700 C) Haldor Topsøe TREMP process Equlibrium curve Operating window +100 C Recycle reduced 50% Lower investment Lower operational cost HP steam T, C % CH4, dry Product spec 20

21 Large temperature increase in 1st reactor benefits recycle cost Inlet T ( C) Exit T ( C) Recycle work (relative) Compressor CAPEX (relative) Base Case Effect of lower exit-temperature Effect of higher inlet-temperature Case Case Case Case Case For TREMP compressor cost is 20% of total investment SNG references Plant Client Capacity Nm 3 /d Year ADAM1 / IRMA NFE, Jülich, Germany ADAM2 demonstration NFE, Jülich, Germany Selected for: SRC2 Stearns Roger, US 1.7 mio (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 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 Undisclosed Illinois, US 2009 Qinghua China 4 mio 2009 Undisclosed (Bio-based) Sweden 2010 POSCO South Korea 2,25 mio

22 Operating experience with MCR-2X Unit Product flow, Nm 3 /hr P, bar Operation, (MSCFH) (psig) 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 demonstration hours Catalyst experience ADAM 1 ADAM 2 Totally more than hours of operation in demo plants and pilots 22

23 High temperature methanation catalyst (MCR) Slight modifications have given an even more stable catalyst 700 Temperature (ºC) h 358 h 1028 h Distance from inlet (cm) ~ Results from Jülich / Wesseling demonstation Reactor designs Isothermal reactors Salt Boiling water Adiabatic reactors Shell cooled Gas cooled reactors Catalyst MCR-2 Demonstrated up to 800 deg. C More shapes MCR-4 23

24 Low-temperature methanation (PK-7R) Used in all Ammonia plants CO and CO 2 are a poison for an ammonia catalyst Used in some of the old H 2 plants CO and CO 2 are a poison for some hydro treating catalysts Haldor Topsøe has ~150 references worldwide Requirement to the feed gas composition Module equations for entrained flow and fixed bed gasifiers M E H CO CO 2 2 CO H CO O C H 2C H M F CO CO O C H C H

25 Feed gas variation harm product quality Feed into methanation plant Module M E H CO 2 2 CO CO Module H CO CO Dry SNG product CH H CO HHV Wobbe Example: Feed gas 30 barg, Methane 0%, 0,75% inerts Requirement to the feed gas impurities Examples for poisons for methanation catalyst Chlorine Arsenic Oxygen Sulphur COS H 2 S CS 2 C 4 H 4 S CH 4 S 25

26 CAPEX estimate Total capacity: Total price: 1,400,000,000 Nm3/a approximately 1.5 billion EUR Syngas generation etc. 65% Rectisol 15% TREMP 10% Sour shift 5% SRU 5% Total 100% (install cost, all inclusive) Summary of TREMP benefits High capacity: Train size above 200,000 Nm 3 /h Max. value of released energy: 85% high-pressure steam (540 C, 140 bar) 140 bar 540 C Up to 3.8 kg / Nm 3 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) 26