Topsoe Activities Downstream Gasifiers

Transcription

1 Topsoe Activities Downstream Gasifiers Poul E. Højlund Nielsen, Klas J. Andersson 8 th International Freiberg/ Conference, June

2 Haldor Topsøe in brief Established in 1940 by Dr. Haldor Topsøe. Private 100% family owned company Global market leader in heterogeneous catalysis with a 75 year long track record 2,700+ employees in 11 countries across five continents. ~900 in production HQ in Lyngby, Denmark. Production in Frederikssund, Denmark and Houston, USA. New factory to open in China in 2015 Three key operating business units: Chemicals, Environmental, and Refinery. A fourth unit, New Business Unit, focused on developing new technologies

3 Examples of Topsøe catalysts Automotive catalysts Stationary DeNOx Ammonia catalyst Sulfuric acid BRIM catalyst Graded bed catalyst

4 Where are Topsøe s catalysts and technologies used? Ammonia Ammonia Automotive Hydrogen Methanol

5 Where are Topsøe s catalysts and technologies used? Oil refineries Ammonia Flue gas cleaning Synthesis gas Sulfuric acid

6 Sources / Raw Materials Gaseous: Natural Gas / Associated Gas / Flare CO 2 Liquid: Naphtha / Heavy Oil Solid: Coal, lignite Biomass Agricultural: Straw, corn stover, molasses, husk Wood: Forestry residues, sawdust, Waste Municipal (> 2bn t/a, urban*) Industrial * WHAT A WASTE, World Bank 2012

7 Syngas conditioning and conversion Gasoline BTX Olefins Propylene DME COAL Gasification Sour shift Methanol Hydrogen (/CO) Formaldehyde COS hydrolysis AGR - Acid Gas Removal Syngas for FT Ammonia SNG Syngas purification Synthesis gas platform

8 Syngas conditioning and conversion Gasoline BTX BIOMASS Gasification Olefins ppmv H 2 S H 2 O + Dusty tar reforming Hot gas filter Propylene DME syngas Filter Clean tar reforming Methanol Formaldehyde Power Sour shift Hydrogen (/CO) COS hydrolysis Syngas for FT Ammonia AGR - Acid Gas Removal SNG Syngas purification Synthesis gas platform

9 Gasification of biomass(or waste) for fuels and chemicals 1. Large scale pressurized gasifiers. 2. Fibrous biomass is difficult to crush into small particles 3. Molten biomass ash is very aggressive (alkali) 4. Leads to fluidized bed gasification 5. Leads to the need for tar reforming and purification.

10 Fluidised Bed Gasifier (bubbling FB ANDRITZ Carbona)

11 Gasifier temperature: 850 C Gasifier pressure: 2MPa Typical gas composition Airblown gasifier CO: 15,9% H 2 S + COS: 40 ppm CO 2 : 12,3% NH 3 + HCN: 1000 ppm H 2 : 14,3% HCl: ppm H 2 O: 12,1% CH 4 : 4,7% CxHy: 0,3% + tar N 2 : 40,3%

12 After the magic tar reformer Approximate gas composition 2MPa, 925 C N 2 : 30-40% CO: 20-30% H 2 : 25-35% CO 2 : 5-10% H 2 O: 10-20% CH 4 : 1-2% NH 3 : ppm HCN: 5-15 ppm HCl: ppm H 2 S: 50 ppm COS: 2 ppm Note H 2 /CO 1

13 Further purification before syngas conversion 1. Sulfur removal to the low ppb level 2. Cl and halogen removal to the low ppb level 3. Conversion of HCN into ammonia and!? 4. Optional removal of ammonia-if acid catalysts are used 5. Removal of trace elements if any, As? 6. Removal of metal carbonyles (Fe, Ni)

14 Sulfur Poisoning of surfaces (Oudar et al)

15 Sulfur on Nickel isotherms I. Alstrup, J.R. Rostrup-Nielsen, S. Røen, Appl. Catal. 1, 303 (1981)

16 Process overview Gasification Plant Process: Andritz/Carbona air blown, low pressure bubbling fluidized bed gasifier Topsoe catalytic tar steam reforming Gas cooling, filtration, and scrubbing Power Plant Process: 3 Gas Engines with heat recovery and 2 Gas Boilers

17 Dusty tar reforming - Skive Fjernvarme I/S Topsoe catalyst and tar reformer operation support initiated 2014: Topsoe revamp of tar reformer + new larger monolith catalyst B. Voss, J. Madsen, J.B. Hansen, K.J. Andersson, The Catalyst Review 29, issue 5, 7-14 (2016)

18 Occasional upstream upsets and catalyst robustness Loading September 2014 Unloading January 2015 B. Voss, J. Madsen, J.B. Hansen, K.J. Andersson, The Catalyst Review 29, issue 5, 7-14 (2016)

19 Skive Fjernvarme about year 2014 The EUDP project "Catalytic tar removal from biomass gasifiers II" resulted in an increased production at the gasification plant, and the year therefore ended above budget. The combined heat and power plant at Marius Jensens Vej has only produced for a few hours during the winter.

20 Black Liquor to Green DME Demo Piteå/Sweden > 3 years of operation New MeOH technology! CO2 Black Liq. AGR DME Unit Sour shift Sulphur Guard MeOH Synthesis Water

21 GoBiGas BioSNG The world s smallest SNG plant

22 BioSNG production overview COS hydrolysis Olefin saturator HTS No S/DG limitation Haldor Topsøe A/S Scope Adsorber

23 Wood2Gasoline BioGasoline

24 Overview of project Gasifier Scrubber Morphysorb Tigas Off-gas Wood chips Gasoline Oxygen steam Clean Tar reformer Sulfur guard Water

25 Trace component Topsøe clean-up steps at GTI HTZ NT-101 CT-101 ST-101 Absorbent for bulk S removal, and hydrolysis of COS/HCN. NH 3 absorbent. Carbonyl guard absorbent. Sulfur polisher and As guard.

26 Wood2Gasoline achievements Results: hours of tar reformer operation gallons gasoline product RON = 97, MON =86 Independent engineer approval: October 2013 Engine Emissions Testing Toxicology review of gasoline components approved by Phillips66 Gasoline testing by SwRI: 80/20 blend found to be substantially similar to conventional gasoline. Fleet Testing 2 Camry s (2.5 L PFI), 2 Corollas (1.8 L PFI) 2 F-150 s (3.5 L V6 EcoBoost ), 2 Fusion s (1.5 L EcoBoost )

27 World s largest synthetic gasoline plant 15,500 bpd gasoline Qinghua-1, China, Inner mongolia 2,500 bpd GSK-10 for 5 Chinese plants Market leader in gasoline catalyst 162 t GSK-10 for Turkmengaz

28 Take home messages Opportunities in biomass gasification gas conditioning Tar steam reforming available and industrially demonstrated for biomass gasification. Gas cleaning before syngas conversion demonstrated Conversion of biomass into gasoline, methanol and SNG demonstrated.