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

AmmoniaAmmonia Automotive

Hydrogen Methanol

Where are Topsøe’s catalysts and technologies used?

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.

Fluidised Bed Gasifier (bubbling FB ANDRITZ Carbona)

www.andritz.com

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)

Sulfur Poisoning of surfaces (Oudar et al)

Sulfur on Nickel isotherms

I. Alstrup, J.R. Rostrup-Nielsen, S. Røen, Appl. Catal. 1, 303 (1981)

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 !

GoBiGas BioSNG – The world’s smallest SNG plant

BioSNG production overview

Haldor Topsøe A/S Scope

COS hydrolysis

Adsorber

HTS No S/DGlimitation

Olefinsaturator

Wood2GasolineBioGasoline

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

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.