POx and Sour Shift Catalyst Applications

VULCAN Systems Technology (POx) Partial Oxidation and Sour

Shift Catalyst Applications

A Business Unit of GBH Enterprises, Ltd.

Gerard B. Hawkins Managing Director

Coal

An expanding market for catalysts and

absorbents


Worldwide Energy Use



Wyoming Low-S Coal Mountain

80 ft wall of coal seam, Powder Rive basin = 40% of US Coal used today; 100yr supply


Products from Coal

• Power • Conventional combustion • Integrated Gasification Combined Cycle (IGCC)

• Ammonia • Methanol • Hydrogen • FT Liquids • Substitute Natural Gas (SNG)


Gasification applications

Power - IGCC

Air Sep

Gasifier Gas Cleaning

Sulfur Removal

Power Turbine

Air

Coal

Sulfur Flue Gas

Power


Gasification for Power - IGCC

Demo units – 300 MW USD 300 million



Power with CO2 Sequestration

Air Sep

Gasifier Sour Shift

Acid Gas Removal

Power Turbine

Air

Coal

Sulfur + CO2

Flue Gas

Power


Coal to Chemicals

Synthesis Gas

Air Sep

Gasifier Sour Shift

Acid Gas Removal

Air

Coal

Sulfur + CO2

Methanol

FT

Ammonia

Hydrogen


Regional variations • China – methanol, ammonia fuels

• USA - SNG

• India - fuels

• Australia - ?

• Europe – biomass gasification


• A fossil fuel with low H/C composition – Means that added H2 needed to utilize it – Energy density is low – More CO2/KW of energy produced than other fossil

fuels • Many impurities that should be removed

– Hg, S-oxides, NOx, ash, heavy metals, Se, As – US gets 52% of its electricity from coal

• Contributes to 60% of total SO2, 33% of Hg, 25% of NOx, and >33% of CO2 emissions

– China gets >90% of its electricity from coal • Will China widely adopt emission controls?

• CO2 does not have a clear cost-effect link – China will be the biggest emitter of CO2 in 2025

• Will China adopt CO2 emission controls?

Issues with Coal


VULCAN Systems Capability

Sour shift • Catalyst supplier for this duty • Many years of successful experience

Purification

• Flexibility to adapt absorbent to specific requirements for COS / H2S, Mercury, Arsenic

Methanol technology

• Catalyst supplier

SNG technology




Feedstocks

• Coal – China, USA

• In situ coal – Australia

• Tar sands - Alberta

• Heavy oil – not economic

• Biomass – future opportunity



Synthesis Gas

Air Sep

Gasifier Sour Shift

Acid Gas Removal

Air Sulfur + CO2

Methanol

FT

Ammonia

Hydrogen


Gasification Technology Suppliers • GE / Texaco • Shell • ConocoPhillips • Siemens (Future Energy) • Choren • Lurgi • Advantica • Chinese


Air Separation Technology Suppliers • Praxair • Air Products • Linde • Air Liquide


Acid Gas Removal Technology Suppliers • Linde (Rectisol) • Lurgi (Rectisol) • UOP (Selexol) • BASF (MDEA)


Technology Suppliers

E-Gas

Slag

Raw gas

Coke

Slurry

Quenchwater

Krupp-Uhde/Shell

Raw gas

HRSG

Burner

Slag

Coolingscreen

Burner

SlagRaw gas

Burner

Raw gasSlag

Refractorylining

FUTURE ENERGY Texaco Conoco Phillips/


Technology Suppliers

FUTURE ENERGY GmbH Chevron Texaco Shell / Krupp-Uhde Conoco Phillips / E-Gas

Cooling screen Cooling wall Shell / Prenflow Shell

Feed fuel coal, ash containing materials

oil,

ash free materials coal oil coal oil coal, residues

Fuel feeding system pneumatic, slurry slurry pneumatic slurry (50 – 70 % coal)

Fuel ash content > 1% < 1 %

Slag molten, granulated molten, granulated molten, granulated molten, granulated

Pressure up to 80 bar up to 80 bar up to 40 bar up to 80 bar up to 40 bar

Capacity up to 500 MW up to 500 MW up to 500 MW

Reactor lining cooling screen cooling wall (refr. lining) refractory lining partial cooling

screen refractory lining refractory lining

Relining interval 10 years 5 years 1 – 2 years 5 years 5 years 5 years

Reactor heat loss 1 – 5 % low medium low low low

Quench / gas cooling total quench radiant heat exchanger

total or partial qu. radiant heat exchanger

total quench/radiant heat exch. (dependent on feedstock)

integr. radiant HE and pre-cooling

by syngas

total or partial qu. external radiant heat exchanger

pre-quench (2nd gas. stage) on coal slurry (900 - 1000 °C)

Start-up time 1 hour 3 days 3 days 3 days 3 days

Availability (single gasifier) 90 - 95 % 95 % 85 % 95 % 70 – 80 % 95 % 70 % Carbon conversion rate > 99 % > 99 % > 84 % > 99 % > 94 %

Cold gas efficiency 78 - 83 % 83.5 % 70.5 % 83 % 83.5 % 84.0 %

Reference plants (number) 5 plants 130 licenses / 72 plants 85 plants 1 plant

Gasification for Ammonia / Methanol Chinese project using Shell technology



GSP gasifier building at Schwarze Pumpe


Technology Suppliers Choren…

• Biomass to FT diesel

• Part-owned by Shell

• Building demo plant


Choren demonstration plant in Freiberg


Technology Suppliers Lurgi…

• Long history

• Alberta hydrogen project

• European research efforts


High pressure test gasifier at Freiberg


Use of VULCAN Sour Shift System

Increases hydrogen production

Produce syngas suitable for ammonia or methanol production

Produce syngas for methanation to SNG

Converts COS to H2S

Converts HCN to NH3


Partial Oxidation Process

Oil or Coal

Condensate

Oxygen

Quench Chamber

Soot Scrubber

Sour Shift Beds

Syngas Product

Gasifier


Catalyst Impact on Shift System Design

VIG SGS-201/202/203 operates over a wide range of steam ratios

VIG SGS-201/202/203 achieves maximum CO conversion, as determined by reaction equilibrium

VIG SGS-201/202/203 resists the possibility of methanation

VIG SGS-201/202/203 operates with a wide range of sulfur in the feed


Dew point flexibility

VIG SGS-201/202/203 is active enough to operate within + 30-50 deg C of the gas dew point and give high CO conversion


Sulfur & Shift Equilibrium

Metal-S + H2O Metal Oxide

+ H2S

Sulfur Tolerant Shift Catalyst

Sulfur Requirement/Catalyst Hydrolysis

-Catalyst to remain Sulfided for Maximum activity

- Steam/Sulfur ratio and temperature critical


Steam Requirement

VIG SGS-201 /202/203 can operate at low steam ratio without risk of methanation: CO + H2O CO2 + H2

CO + 3H2 CH4 + H20

Likely to require a steam : CO ratio of 2.0


Effect of Trace components

COS - converted to H2S (COS hydrolysis) Metal carbonyls - decomposed and

deposited as sulfides (FeS/NiS) Nitrogen compounds - HCN almost

completely removed Halogens - catalyst not affected at typical

concentrations C, dust - deposited on catalyst

A Business Unit of GBH Enterprises, Ltd. www.gbhenterprises.com

Catalyst Attributes

high mechanical strength to resist external fouling, water impingement

resist deposit build-up stability to withstand high steam partial pressure at

high temperature high activity - low CO, close approach to shift

equilibrium operation close to dew point - occasional wetting low pressure drop - minimum pressure drop

increase


Robustness/Regenerability

Maximum physical robustness

Can be regenerated if Carbon/Coke like polymer formation

Partial activity recovery


Operating Experience

Long lives • Upstream bed : 2 - 5 years • Downstream bed : 3 - 7 years

Operating Temperature • Normal : 200 - 500 deg C • Excursions up to 550 deg C

Operating Pressures • Experience with wide pressure range • Up to 80 bar • Tested successfully up to 100 bar • Can tolerate high steam partial pressure ~ 50 bar


Resistance to Fouling

SHIFT CATALYST


Trap for Deposits and contamination

Catalyst Developments

Improved activity variants - smaller

reactors, higher CO conversion

Lower pressure drop - optimization of particle size/shape

Manufacturing at new locations


Catalyst Developments - Geometry

Particle size / shape optimisation

scope to lower initial pressure drop and rate of pressure drop increase

potentially some small impact on activity

options for radial flow configurations


Catalyst Developments - VIG SGS-201/202/203

- High activity sour gas shift catalyst - CoO/MoO3 on MgO/Al2O3 support


Catalyst Developments - VIG SGS-201/202/203

Higher external surface area to trap poisons good resistance to impurities including

heavy metals (Pb, Hg, As) and soot Higher voidage

lower pressure drop High thermal resistance & high mechanical

strength slow rate of PD increase

Optimized loading with VIG SGS-202, VIG SGS-203 and AST Support to suit requirements


Conclusion – Sour shift

Requirement for POX increasing in response to several factors

Potential for successful integration of Sour Shift application with gasification technology

Opportunities to build on success of VIG SGS-201/202/203 with developments to meet particular client needs


Conclusions

GBH Enterprises have a leading position in supplying technology, catalysts and absorbents for gasification applications

• Full capability for sour shift, purification and methanol synthesis


Date post:	02-Nov-2014
Category:	Technology
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