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Topsoe Activities Downstream Gasifiers
Poul E. Højlund Nielsen, Klas J. Andersson8th International Freiberg/ Conference, June 12-16 - 2016
Haldor Topsøe in brief
• Established in 1940 by Dr. HaldorTopsøe. 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
Examples of Topsøe catalysts
Ammoniacatalyst
Automotivecatalysts
Sulfuricacid BRIM™
catalyst
StationaryDeNOx
Graded bedcatalyst
AmmoniaOil refineries Flue gas cleaning
Synthesis gas Sulfuric acid
Where are Topsøe’s catalysts and technologies used?
Sources / Raw Materials
Gaseous: Natural Gas / Associated Gas / Flare CO2
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
DME
Formaldehyde
Gasoline
BTX
Propylene
Olefins
Hydrogen (/CO)
Ammonia
Methanol
Syngas for FT
SNG
Syngas conditioning and conversion
COAL Gasification
Sour shift
COS hydrolysis
AGR - Acid Gas Removal
Syngas purification Synthesis gas platform
Syngas conditioning and conversion
BIOMASS Gasification
Cleantar reforming
Dustytar reforming
Sour shift
COS hydrolysis
AGR - Acid Gas Removal
Syngas purification
Hot gasfilter
Filter
Hydrogen (/CO)
Ammonia
Methanol
Syngas for FT
Synthesis gas platform
DME
Formaldehyde
Gasoline
BTX
Propylene
Olefins
SNG
Power
10-200 ppmv H2SH2O +
syngas
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.
Airblown gasifier
• Gasifier temperature: 850°C• Gasifier pressure: 2MPa• Typical gas composition
• CO: 15,9% H2S + COS: 40 ppm• CO2: 12,3% NH3 + HCN: 1000 ppm• H2: 14,3% HCl: 10-100 ppm• H2O: 12,1%• CH4: 4,7%• CxHy: 0,3% + tar• N2: 40,3%
After the ”magic” tar reformer Approximate gas composition
2MPa, 925°C N2 : 30-40% CO: 20-30% H2: 25-35% CO2: 5-10% H2O: 10-20% CH4: 1-2% NH3: 300-500 ppm
HCN: 5-15 ppm HCl: 10-100 ppm H2S: 50 ppm
COS: 2 ppm Note H2/CO 1≅
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)
Power Plant Process:– 3 Gas Engines with heat recovery
and 2 Gas Boilers
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
Dusty tar reforming - Skive Fjernvarme I/S
• 2009- 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)
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)
Skive Fjernvarme about year 2014
“The EUDP project "Catalytic tarremoval from biomass gasifiers II"resulted in an increased production atthe gasification plant, and the yeartherefore ended above budget. Thecombined heat and power plant atMarius Jensens Vej has only producedfor a few hours during the winter.”
Black Liquor to Green DME Demo – Piteå/Sweden
CO2Black Liq.
Water
Sour shift
Sulphur
Guard
MeOH Synthesis
AGRDME
Unit
> 3 years of operation
• New MeOHtechnology !
BioSNG production overview
Haldor Topsøe A/S Scope
COS hydrolysis
Adsorber
HTS No S/DGlimitation
Olefinsaturator
Overview of project
Woodchips
Oxygensteam
Off-gas
Gasoline
Water
Gasifier
CleanTar reformer
Scrubber Morphysorb Tigas
Sulfurguard
Trace component Topsøe clean-up steps at GTI
HTZ
Absorbent for bulk S removal, and hydrolysisof COS/HCN.
NT-101
NH3 absorbent.
CT-101
Carbonyl guardabsorbent.
ST-101
Sulfur polisher and As guard.
Wood2Gasoline achievements
• Results:• +1.000 hours of tar reformer operation• +10.000 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®)
World’s largest synthetic gasoline plant
15,500 bpd gasoline
GSK-10 for 5 Chinese plantsMarket leader in gasoline catalyst162 t GSK-10 for Turkmengaz
Qinghua-1, China, Inner mongolia2,500 bpd