The Low Cost Gas Era Gasification versus Steam Reforming - a True Alternative?

Karsten Radtke, Ines Wulcko ThyssenKrupp Industrial Solutions (USA/Germany)

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ThyssenKrupp Group: - founded 204 years ago in Essen (Krupp) TKIS: - 100+ gasifiers designed, built, put into successful operation - world leader in syngas technologies: Gasification (PRENFLO, HTW), Steam Methane Reforming (SMR), Auto Thermal Reforming (ATR)

Sales: US$ ~46 bn Employees: 160,745

ThyssenKrupp Group

Industrial Solutions (TKIS)

Components Technology

Materials Services

Steel Americas

Elevator Technology

Sales (€ mill) 6,172

EBIT** (€ mill) 268

Employees 28,941

Sales (€ mill) 6,416

EBIT** (€ mill) 674

Employees 50,282

Sales (€ mill) 6,271

EBIT** (€ mill) 420

Employees 18,546

Sales (€ mill) 13,660

EBIT** (€ mill) 212

Employees 30,289

Steel Europe

Sales (€ mill) 8,857

EBIT** (€ mill) 206

Employees 26,231

Sales (€ mill) 2,060

EBIT** (€ mill) -68

Employees 3,466

*) Continuing operations (after reclassification of Steel Americas) before consolidation **) Adjusted before consolidation, after definition changes

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Shale Gas: Challenge and Opportunity for Synthesis Gas Generation

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Synthesis Gas is the central intermediate product: Nearly all hydrocarbons can be converted to syngas – by very different means

Gas, Naphtha

Oil/Residues

Steam Reformer / ATR

HTW Gasification

Synthesis Gas

CO + H2

Methanol

Ammonia

IGCC

Fischer-Tropsch

CO- Shift

Methanation

Diesel, Plastics

Gasoline, LPG

Urea

Diesel, Naphtha

Petcoke

Hard Coal

Biomass

PRENFLO Gasification

Biomass

Lignite

Wastes

Waxes, Lubes

MTO

MTG

Feedstock Hydrocarbon

Conversion Syngas Product Product Generation

Hydrogen

Synthetic Natural Gas

El. Power

Fertilisers

Oil Gasification

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Entrained-Flow Gasification

Fluidized Bed Gasification

Steam Methane Reforming

Autothermal Reforming

PRENFLO ® HTW ™ SMR ATR

PSG

ThyssenKrupp Industrial Solutions: Proprietary Syngas Technologies

PDQ

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Entrained-Flow Gasification: PRENFLO

PRENFLO is a slagging gasifier that operates

above the ash melting point

=> high carbon conversion, high efficiency

for coal and petcoke

for biomass , if pre-treated

Major Reference: Elcogas IGCC, Puertollano/Spain

Selected and permitted for several projects

around the world, including U.S.A.

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Uhde PRENFLO gasification under construction: BioTfueL in France

• Biomass/Coal/Petcoke/Oil Gasification to Liquid Fuels Facility

• Construction ongoing • Commissioning starts in 2016 • Start-up beginning 2017

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Fluidised-Bed Gasification: Uhde HTW Gasification

HTW especially suited for biomass, wastes and low-rank,

high ash coals with high ash melting points

HTW has strong reference basis through full

commercialisation over 3 decades

New HTW Pilot Plant at University Darmstadt commissioned

in 2015

Current main focus on China, India

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• More than 60 Uhde steam reformers built since 1966

• Largest reformer has 960 tubes

• Commercial reformers operate over a wide range

Ammonia @ 40 bar 780 - 820 °C Methanol @ 20 - 25 bar 850 - 880 °C Hydrogen @ 20 - 25 bar 880 °C Oxogas @ 9 - 12 bar 900 °C Olefins (STAR) @ 5 - 6 bar 570 - 590 °C

SINCOR C.A., Jose, Venezuela 2 x 98,000 m3/h (Vnorm) Hydrogen

Uhde Steam Reforming Technology

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• Pressure bar(a) 5 - 50

• Process steam % 100 ( base case )

• Gas quality - H2 surplus

• Energy available - Excess

• Air separation - -

• Steam ratio - 2.5 - 3.4

• H2-CO2/CO+CO2 - 2.9 - 3.0

• CH4 slip % 3.0 - 5.0

• O2 required Mol/Mol -

C in feed

Steam

NG

Prod. Gas

880°C

Principle Overview: Steam Reforming (SMR)

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Hydrogen Plants, St. Charles, LA & Port Arthur, TX

Two plants with 135 mm SCFD each based on Uhde Steam Reforming technology

Uhde Steam Reforming (SMR) Technology

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Uhde Auto-Thermal Reformer (ATR) Technology

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Principle Overview: Autothermal Reforming (ATR)

• Pressure bar(a) 30 - 40

• Process steam % 70

• Gas quality - Carbon surplus

• Energy available - Energy import for drives

• Air separation - Required

• Steam ratio - 0.3 - 3.5

• H2-CO2/CO+CO2 - 1.1 - 1.7

• CH4 slip % 0.5 - 4.0

• O2 required Mol/Mol 0.55 - 0.75 C in feed

Prod. Gas

1,000°C

Steam

300°C

O2

100°C

NG

580°C

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Combined Reforming (SMR plus ATR)

• Pressure bar(a) 40

• Process steam % 60 - 65

• Gas quality - Stoichiometric

• Energy available - Energy import for drives

• Air separation - Required

• Steam ratio - 1.5

• H2-CO2/CO+CO2 - 2.02

• CH4 slip % 1.0

• O2 required Mol/Mol 0.445 C in feed

780°C Prod. Gas

880°C

O2

100°C

NG

370°C

NG

510°C

Steam

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Combined Autothermal Reforming (CAR®)

• Pressure bar(a) 40

• Process steam % 100

• Gas quality - Stoichiometric

• Energy available - Energy import for drives

• Air separation - Required

• Steam ratio - 2.5

• H2-CO2/CO+CO2 - 1.98

• CH4 slip % 1.0

• O2 required Mol/Mol 0.49 C in feed

O2

100°C

Prod. Gas

550°C

NG

370°C

Steam

300°C

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Main chemical reactions for synthesis gas generation: Steam reforming CH4 + H2O → CO + 3 H2 ΔHR = +206 kJ/mol endothermal Partial oxidation: CH4 + 0.5 O2 → CO + 2 H2 ΔHR = -35 kJ/mol exothermal

Synthesis gas composition requirements:

• ammonia: (H2 + CO) / N2 ≈ 3.0

• methanol: (H2 – CO2) / (CO + CO2) ≈ 2.0

• hydrogen: H2 = max.

• gas to liquids: H2 / CO ≈ 2.0

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Syngas Technologies in Comparison: H2/CO Ratio

Hydrogen production is favored by SMR, other technologies such as ATR/CAR/POX produce more CO or lower H2/CO ratios

SMR has economical advantages in producing hydrogen for large capacities

Syngas applications, which require more CO content, are favored by the non-SMR routes, especially by Partial Oxidation/Gasification

SMR

Combined Reforming

ATR

Oil/Gas Gasification

Coal Gasification

0 1.0 2.0 3.0 4.0

Note 1): H2/CO ratio adjustable via CO Shift

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Steam Reformer Technologies: Summary Overview

Steam ref. ( 1 ) Combined ref. ( 2 ) CAR ( 3 ) Autoth. ref. ( 4 )

• Pressure bar(a) 5 - 50 40 40 30 - 40

• Process steam % 100 ( base case ) 60 - 65 100 70

• Gas quality - H2 surplus Stoichiometric Stoichiometric Carbon surplus

• Energy available - Excess *) Energy import Energy import Energy import for drives for drives for drives

• Air separation - - Required Required Required

• Steam ratio - 2.5 - 3.4 1.5 2.5 0.3 - 3.5

• H2-CO2/CO+CO2 - 2.9 - 3.0 2.02 1.98 1.1 - 1.7

• CH4 slip % 3.0 - 5.0 1.0 1.0 0.5 - 4.0

• O2 required - - 0.445 0.49 0.55 – 0.75 (Mol/Mol C in feed)

*) No excess in case of an additional pre-reformer

300°C 510°C Steam

NG

880°C

Steam

780°C 880°C

100°C

370°C

NG

NG

O2

O2

Prod. Gas

NG

Steam

Prod. Gas

Steam

O2

NG

370°C

550°C

100°C Prod. Gas

580°C

100°C

580°C

1,000°C

1 2 3 4

Prod. Gas

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Gasification Partial

CO Shift AGR MeOH synthesis

MeOH

ATR

Offgas

85% 15% to Aux. Boiler Example 1: Coal-to-MeOH

Example 2: Coal-to-NH3

CO Shift

AGR PSA

ATR

Offgas

85% 15% to Aux. Boiler

NH3 synthesis

NH3

Combination Gasification with Auto-Thermal Reforming

Gasification

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SMR ATR HTW

HTW

with

ATR

PRENFLO

Steam ratio (volume based) 2.5 - 3.4 0.3 - 3.5 - - -

H2/CO-ratio 3.0 - 5.0 2.0 - 5.0 0.76 1.13** 0.58

Syngas ratio (H2-CO2)/(CO+CO2) 2.9 - 3.0 1.1 - 1.7 0.15 0.37** 0.36

CH4 slip (% of water and N2 free raw gas) 3.0 - 5.0 0.5 - 4.0 5.68 4.45** 0.01

Feed consumption (MW Feed/1000 Nm³/h

Syngas)* 3.0 - 4.0 3.6 - 4.2 5.00 3.71 4.26

Steam consumption (kg Steam/Nm³/h Syngas) * 0.756 *** 0.1 - 1.0 0.27 0.30 0.02

O2 consumption kg O2/Nm³ Syngas * - 0.3 - 0.5 0.38 0.32 0.43

* Syngas = CO + H2

** Values after merging the syngas originating from HTW and ATR, before CO-shift) *** Steam input, SMR: actual net steam consumption: 0.276 kg steam/Nm³ syngas

Characteristics of Gas Generation Technologies Key Performance Parameters

Gasification

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Syngas Technologies: Summary

Solid or liquid feedstocks require Gasification Technology to generate syngas. Steam Reforming, Auto Thermal Reforming or Combined Autothermal Reforming are only applicable for gaseous feestocks.

For gas feedstocks, the desired product influences the technology decision: Hydrogen production prefers the application of SMR technology High CO containing gas applications prefer gasification/partial oxidation SMR has economical advantages in producing hydrogen for large capacities

The combination of Gasification (HTW) with Reforming (ATR) provides higher product yield from the same amount of coal feedstock, higher H2/CO ratio, and reduces the consumption figures, and increases the feedstock flexibility (solid/gas)

Gasification has a broad feedstock flexibility. Once the plant is installed, only gasification allows the later application or variation of alternative feedstocks – if properly foreseen during the design stage (e.g.: BioTfueL)

The oil & gas price volatility over the life-time of a chemical plant (typically 25+ years) is far less predictable than the coal price stability

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Gasification IGCC Plant

Puertollano, Spain October 2015

Steam Reforming PDH/PP Complex Port Said, Egypt October 2015

Thank you for your attention