A syngas network for reducing industrial carbon footprint and

energy use

Professor Dermot J Roddy

Newcastle University

www.ncl.ac.uk/energy

Sustainable Thermal Energy Management in the Process Industries International Conference (SusTEM2011)

The basic proposition

There is a case for building syngas (or synthesis gas) networks as a means of contributing to the reduction of industrial carbon footprints.

What is syngas?

• To a chemist: H2 + CO

• Usually also contains CO2

• Often contains methane

• Contaminants: H2S, COS, particulates, tars, nitrogen compounds

• Composition depends on feedstock, gasification conditions, choice of gasification technology, choice of oxidant, extent of clean-up

Outline of presentation

• Syngas from fossil fuels

• Syngas from sustainable sources

• Syngas for power, heat, fuels & chemical feedstocks/products

• CO2 capture & storage?

• Pathways that reduce net energy footprint or CO2 emissions

• The case for building a syngas network

• Syngas network development – the issues.

Syngas from fossil fuels

Eston Grange 850MW IGCC plant with CCS

Syngas from fossil fuels

UCG

Composition % v/v Contaminants g/m3

Hydrogen 61 Dust Nil

Methane 25 Ammonia 0.1

Carbon monoxide 5 Naphthalene 0.5

Carbon dioxide 2 Benzole 4 – 15

Ethane 1 Hydrogen Sulphide 1 – 5

Ethylene 2 Hydrogen Cyanide 0.1 - 5

Nitrogen 4

Oxygen 0.2

Coke oven gas

Syngas from sustainable sources

Syngas from sustainable sources

Gussing plant, Austria

Syngas for power, heat, fuels & chemical feedstocks/products

Methanol synthesis

Copper-zinc

catalyst

220-300°C

50-100bar

Methanol

Mixed alcohols synthesis

Alkali-FT or Alkali-

methanol catalyst

260-425°C

30-300bar

Mixed alcohols:

methanol,

ethanol and

higher alcohols

Syngas fermentation

Biological:

anaerobic

microbes

20-40°C

Atmospheric

Ethanol and/or

other alcohols

Fischer-Tropsch synthesis

Iron or cobalt

catalyst

200-350°C

20-40bar

Heavy waxes for

diesel, or light

olefins for

gasoline

E4Tech, Review of technologies for gasification of biomass and wastes, 2009,

NNFCC project 09/008, available via www.nnfcc.co.uk.

Teesside Chemicals Cluster

North Sea Crude

Refinery 6)

Petroplus

Feedstock, inputs

various

Natural gas

various

Olefins (cracker)

Huntsman

Aromatics Huntsman

Ammonia Terra

Nitric Acid Terra

Acrylics Lucite

Alkylamines

Nitrobenzene Huntsman

PTA DuPontSA

PET DuPontSA

Olefin exports

EO/EG Dow

By Product 3)

HCN BASF

EOD Dow

Ethoxylates Uniqema

Abbreviations:

AN: Acrylonitrile ADN: Adiponitrile HMDA: Hexamethylenediamin ACN: Acetonitrile ACH: Acetone Cyanohydrin HCN: Hydrogen Cyanide EO/EG: Ethylene Oxide/ Ethylene

Glycols EOD: Ethylene Oxide Derivatives PET: Polyethylene Terephthalate PTA: Purified Terephthalic Acid KA: Ketone Alcohol AA: Adipic Acid

Key:

Product PTA

Company DuPontSA

Olefins Chain

Aromatics Chain

Ammonia Chain

ACH 2)

Lucite

Export ACN 1)

BP

AN BASF

HMDA BASF

ADN BASF

Aniline Huntsman

KA 4)

DuPont AA DuPont

Nylon 6,6 DuPont

HMDA 5)

DuPont

Propylene

Ethylene

Ethylene

Propylene

Cyclohexane

Benzene

Paraxylene

EO

EO

EG

Cyclohexane

ADN

Ethoxylates Shell

EO

Natural Gas

Olefins (cracker) Sabic

Aromatics

Sabic

Ammonia

Terra

Nitric Acid Terra

Nitrobenzene

Huntsman

PTA

Artenius

PET

EO/EG

Dow

HCN

BASF

Ethylene Oxide Derivatives

Dow

Ethoxylates

Croda & Shell

Abbreviations:

HMDA: Hexamethylenediamine

ACH: Acetone Cyanohydrin HCN: Hydrogen Cyanide EO/EG: Ethylene Oxide/ Ethylene

Glycols

PET: Polyethylene Terephthalate PTA: Pure Terephthalic Acid KA: Ketone Alcohol

Polyester

Polyurethanes

ACH

Lucite

Acrylonitrile

BASF HMDA BASF

Adiponitrile BASF

Aniline

Huntsman

KA Invista Adipic Acid

Invista Nylon 6,6

Invista

HMDA Invista

Propylene

Ethylene

Benzene

Paraxylene

North Sea

Crude Oil

Cyclohexane

Adiponitrile

Nylon

MMA Lucite

Acrylics

Distillation

Petroplus

Hydrofining

Petroplus

Diesel blending

Petroplus

Imported Naphtha

LPG & Naphtha

Ethylene Oxide

Ethylene Glycol

Nitram

Terra

Artenius

Imported Acetone

Surfactants

Croda

Imported Feeds

Natural Gas

Byproduct HCN

Higher Alcohols

MMA: Methyl Methacrylate

LPG: Liquid Petroleum Gas

Fertiliser

Teesside Chemicals Cluster

How pure does syngas need to be?

Adapted from: ] Roddy, DJ and Manson-Whitton, C, Biomass gasification and pyrolysis. In Comprehensive Renewable Energy, Volume 5: Biomass and Biofuels, Elsevier, March 2012 (in press)

Raw syngas Engine Chemical synthesis Sulphur (mg/Nm3)

750 50 0.1

Halides (mg/Nm3)

15 0.1

Particulates (mg/Nm3)

2500 15 0.001-0.01

CO2 capture from syngas

Combined Cycle

Gas Turbine

Feedstock Steam

Gasification

Plant

Heater

Boiler Feedwater

Frit Gas Turbine

Heat Recovery Steam Generator

Steam Turbine Boiler Feedwater

Gas Treatment Sulphur and CO2 Removal ASU

Oxygen

Air

Nitrogen

S

S

CO2 gas

Entrained

Flow

Quench

Gasifier

Sulphur

Technologies for CO2 separation

Chemical absorption eg mono-ethanolamine Developed in 1940s

Physical absorption eg pressure swing

absorption

Mature technology

Membranes eg cellulose acetate,

polydimethylsiloxane,

polyvinyl alcohol

Compact, simple, low

maintenance & energy

efficient. Working on

selectivity, permeability &

cost.

Size Technology of choice today

Very small

<5 million scfd

Membrane units

Small

5-40 million scfd

Amine and membrane units

compete

Medium/large

>40 million scfd

Amine units are cheaper

Basile, A, Gallucci, F and Morrone, P, Advanced carbon dioxide (CO2) separation membrane development for power plants, in Advanced power plant materials, design and technology, 2010, DJ Roddy (ed), Woodhead Publishing.

CO2 capture & storage?

Pathways that reduce net energy footprint or CO2 emissions

• Where the original source of the syngas is sustainably grown biomass

• Where the original source of the syngas is waste oils, flare gases or other carbonaceous industrial wastes

• Where syngas is decarbonised and used for power generation or hydrogen displacement

• Where CO2 is captured during syngas conversion (eg to ammonia)

• Where syngas is converted into long-life polymers

• Carbon-negative combinations?

The case for building a syngas network

• Carbon floor price is coming • Energy-intensive industries in the UK are struggling

to secure Government support (except possibly for the electricity-intensive industries)

• There are options for reducing energy footprint & CO2 emissions using syngas

• Relevant plants are spatially distributed in regional clusters – so a network is needed

• The same concept applies to other process industry clusters around the world with the same or similar drivers.

Buffer storage

F

F Heat

exchanger

Brine Heater

Steam

Condensate

Condensate

Hydrogen out

Hydrogen

in

Brine Reservoir

Steam

300 –

400m

Hydrogen

Brine

F: Duplicated product

flow meter

Not shown: Emergency

shutdown system

Knockout pots

Filters

Syngas network development – the issues

• Sizing the network

• Timing its growth

• Determining ownership & access arrangements

• Planning & regulatory hurdles

• Wide range of “syngas” compositions.

Questions?

Professor Dermot J Roddy Newcastle University

dermot.roddy@ncl.ac.uk www.ncl.ac.uk/energy

Funding from the Regional Development Agency for

North East England (One Northeast) and the Tees Valley Industrial Programme for exploring the regional

implications of this work is acknowledged.