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Hydrogen Supply and Sulfur Removal for the Modern, Environmentally Low-Impact Refinery

Middle East Downstream Week

Abu Dhabi, 8-11 May 2011

Phil Morris and Uday N. Parekh , Air Products Elmo Nasato – Goar, Allison & Associates, Inc

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Presentation Outline

Introduction

Hydrogen Supply

– Air Products / Technip Alliance

– Technology Advances

– Energy Efficiency Improvements and CO2 Emissions Reduction

Hydroprocessing and Implications on the Sulfur Block

– SRU Oxygen Enrichment – Theory, Technologies

– Scenario Analysis

– Implementation

Grassroots Oxygen-based SRUs

– Capital and Operating Expense Analysis

– Emission Reductions

Conclusions

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Refinery Hydrogen Growth

Hydrorefining

H2

Heavy / Sour

Crude Light / Sweet

Crude

Transportation

fuel 42%

Other 24%

Residual fuel 34%

H2 Nm3/m3 0 – 25

Sulphur spec. > 1000 ppm

Low conversion

refinery

Other 17%

Transportation

fuel 82%

Residual fuel 1%

H2 Nm3/m3 700 – 1000+

Sulphur spec. <30 to <10ppm

High conversion

refinery

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Air Products & Technip:

#1 Suppliers to the Refining Industry

Alliance established in 1992 to design and build Air Products on-site H2 plants

Technip is #1 supplier of hydrogen equipment to refining industry

Technip brings proven SMR design, detail engineering skills

Technip designs and modifies H2 Plants to Air Products’ Standards

Air Products brings separation technology, process integration, process controls and operations experience

Joint development initiatives bring project execution efficiencies

Alliance has executed >30 projects

Outsourcing has grown from approximately 100 kNm3/h in 1992 to 6 million Nm3/h today

Air Products

2,556 kNm3/hr

~43%

On-stream 2010 - 5,945 kNm3/hr

Tonnage Hydrogen

www.h2alliance.com

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Design Optimisation

Major advancements in catalysts and tube metallurgy

– Increased reformer severity

– Higher combustion air preheat

– Increased average heat flux

Mechanical design advancements to improve long term integrity and performance optimisation

Modern day H2 plants compared to equivalent 1990s plant:

– 10-20% more capacity

– > 5% higher energy efficiency

– Higher reliability and better operational flexibility

The Alliance has been the forerunner in the application of pre-reforming technology with more than 40 units to Technip’s credit

– Air Products was the first industrial gas company to apply it in a large hydrogen plant on multiple feedstocks

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Captive Steam Power Synergy

Typical H2 plants are large exporters of steam and this is not always required by a refiner

– Cogeneration of power from this steam can be attractive

• Under certain fuel power price scenarios

• Insufficient or unreliable power grid supply

Grassroots or refineries undergoing major upgrades or expansion require substantial captive power and steam

– Integrate gas turbine with the H2 plant which will reduce costs and improve the overall CO2 footprint

GT exhaust is integrated with the H2 plant as hot combustion air for the furnace with the excess sent to a separate HRSG for extended steam power synergy

– Example – 100 kNm3/h H2 plant with 30 MW GT providing up to 75 MW and export steam

• CO2 can be lowered by 15-20% vs standalone units

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Port Arthur II

Integrated SMR/Cogen

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• Advanced ROG integ.

•Exten. Pre-reforming

•Enhanced SMR severity

Hydrogen Technology Map

• SMR no APH

• HTS – PSA

•ROG feed mix

• SMR – Cogen

• GTE integration

H2 T

ec

hn

olo

gie

s P

rog

res

sio

n

Timeline 1994 2012

• Pre-reforming

• APH

• Multi feed Pre-reforming

• High severity SMR

• SMR full GTE-HRSG

• RFG integration

• Max power /steam

• Higher severity SMR

• pre-reforming - MTS

• Advanced heat recovery

• Advanced cycle

•CO2 management

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Hydrogen Plant Efficiency

Improvement Over Two Decades

88

90

92

94

96

98

100

102

Relative H2 Plant

Feed & Fuel %

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Summary

The H2 plant constitutes a substantial part of the energy input in to a refinery

The CO2 release from a deep conversion refinery’s H2 plant could be up to 25% of the total emissions

Technological advancements and continuous improvements are able to appreciably reduce the H2 plant CO2 footprint

18 years of the Air Products/Technip Alliance has yielded an efficiency improvement of 5-7% from an already high threshold

Centralising cogeneration with H2 production through integrated plants can further reduce the CO2 footprint by 15-20% vs standalone units

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Intensive

Hydro

processing

H2

Clean Fuels

An Inconvenient

Consequence !!

On to sulfur recovery >>>>>>

AGR / SRU H2S

O2

Degassing Clean Sulfur

Clean Fuels and High Conversion

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Goar, Allison & Associates

Sulfur Block Process Capabilities

Sulfur Recovery Plants

– SRU Process Design — air based and O2-based featuring COPETM O2 enrichment

Sulfur Processing and Handling

– Featuring D’GAASSTM H2S removal

Tail Gas Cleanup Units

– Amine based systems

Gas Treating Units

– MEA, DEA, MDEA based systems

Sour Water Strippers

– Broad process design capabilities

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Modified Claus Process

Key Reactions

H2S + 3/2 O2 SO2 + H2O (Combustion Reaction)

2H2S + SO2 3S + 2H2O (Claus Reaction)

____________________________________________

3H2S + 3/2 O2 3S + 3H2O (Overall Reaction)

3H2S + 3/2 O2 + 5.6 N2 3S + 3H2O + 5.6 N2

H2S + 3/2 O2 SO2 + H2O (Combustion Reaction)

2H2S + SO2 3S + 2H2O (Claus Reaction)

____________________________________________

3H2S + 3/2 O2 3S + 3H2O (Overall Reaction)

3H2S + 3/2 O2 + 5.6 N2 3S + 3H2O + 5.6 N2

Nitrogen bottlenecks the SRU !!

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Why Oxygen Enrichment

Increases SRU Capacity

25

113

57

169

339

286

50

170

85

84

339

261

100

226

113

0

339

235

20.9 (air)

100

50

189

339

293

Oxygen Enrichment,

%

Acid gas,

kgmol/h

Oxygen,

kgmol/h

N2 + Ar,

kgmol/h

Total flow to reaction

furnace, kgmol/h

Total flow to TGCU,

kgmol/h

Total flow constant;

Acid gas flow increases as O2% increases

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COPE Phase II

SRU Capacity Increase with O2 Enrichment

Three Proven Technologies

0

20

40

60

80

100

120

140

160

180

20 30 40 50 60 70 80 90 100

% C

ap

ac

ity In

cre

as

e

% Oxygen

92% H2S Low Level Enrichment

70% H2S

50% H2S

35% H2S

COPE Phase I

Acid Gas

Concentration

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NATURAL

GAS

COMBUSTION

AIR

PROCESS GAS

MOTIVE STEAM

RECYCLE GAS

EJECTOR

Recycle stream added to

control RF temperature

Enrichment up to 100% O2

Capacity up to 250% of air

based capacity

COPE PHASE II

PROCESS

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COPETM

Process

O2 Enrichment Benefits

Large capital savings for new plants from reduced number and size of SRU trains

Capital cost savings of over 75% for a COPE retrofit versus a new SRU

Potential 100+% capacity increase

Reduces SO2 and CO2 emissions

Reliability, Flexibility and Redundancy

Proven safety

Quick / Staged Implementation

Compact Footprint

Experience

Commercialised in 1985; 25 years of reliable, continuous operation

> 30 units in operation

SRU Capacity Increase with

Oxygen Enrichment

0

20

40

60

80

100

120

140

160

180

20 30 40 50 60 70 80 90 100

% C

ap

ac

ity In

cre

as

e

Mol % Equivalent Oxygen

92% H 2 S* Low Level Enrichment

COPE TM Phase I

COPE TM Phase II 70% H 2 S

50% H 2 S

35% H 2 S

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SRU Oxygen Enrichment Benefits

Lower Emissions

SRU impact

Improved overall sulfur recovery efficiency due to higher partial pressures and conversions in the SRU catalytic reactors – about 0.5% higher

TGCU impact

Reduced flow rates and higher partial pressure of H2S in the TGCU amine absorber lead to lower H2S content in absorber vent stream and hence, lower SO2 emissions

Much smaller vent gas stream (less N2) from the absorber to the incinerator leads to less fuel gas usage and lower CO2 emissions

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Why Oxygen Enrichment

Decreases SRU Emissions

Rich Acid Gas Feed (93.7% H2S)

Air-Based

Operation

COPE Operation

(65% O2)

COPE vs

Air-Based

100 TPD 200 TPD %

Increase Comments

Contained S in Feed, TPD 100 200 100%

SRU Tail Gas Flow, Nm3/h 9,456 8,625 -9%

Contained S in Tail Gas, TPD 2.7 4.2 56%

Feed Gas to TGCU Amine

Absorber, Nm3/h

6,885 2,786 -60%

Feed to absorber

60% lower despite

2X capacity

Absorber Off-Gas to Incinerator,

Nm3/h

6,830 2,625 -62%

Feed to incinerator

62% lower despite

2X capacity

H2S Level in Absorber Off-Gas,

ppmv 80 80 0%

Contained S in Gas to

Incinerator, kg/hr 0.78 0.30 -62%

SO2 Emissions from Incinerator

Stack, TPY 13.68 5.26 -62%

SO2 emissions

62% lower despite

2X capacity!

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SRU Oxygen Enrichment Benefits

Increased Flexibility and Reliability

Improves overall refinery reliability by providing SRU redundancy at much lower costs than building a new SRU

Allows SRU to match changing refinery needs; for example running a sour crude campaign

Better destruction of ammonia, hydrocarbons and BTX — lessened risk of plugged catalyst beds and reduced run length

More robust operation that is more forgiving to upstream unit upsets and throughput changes

For lean acid gas streams, oxygen enrichment improves flame stability and is better than fuel ―spiking‖

Operators love O2 Enrichment once implemented

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Increased sulfur load to SRU for a

heavy, sour crude refinery

New Capacity or

Expansion (bpd)

Naphtha

HDS

Kerosene

HDS

Diesel

HDS VGO HDS Hydrocracker

Sulfur Generated (TPD)

10,000 2.5 10 27 41 48

20,000 5 20 54 81 94

30,000 7.5 30 81 122 142

40,000 10 40 107 163 189

50,000 12 50 134 204 236

60,000 15 60 161 244 283

70,000 17 70 188 285 330

Legend: Oxygen Enrichment Technologies

Low-Level up to 25% SRU Capacity Increase

Mid- Level -- COPE Phase I up to 45% SRU Capacity Increase

High - Level -- COPE Phase II up to 120% SRU Capacity Increase

Crude properties: 21.9 API, 0.92 spec gravity, 3.3 wt% sulfur

Sulfur plant/s capacity: 500 TPD

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Example - Benefits of COPE for a

Grassroots Sulfur Recovery Complex

Basis: 1,200 MTPD total SRU capacity

Air-Based Configuration: Four 400 MTPD SRU and TGCU trains (one train is for redundancy)

Proposed COPE Configuration: Three COPE SRU and TGCU trains (sized approx 300 MTPD air-based), each capable of a maximum capacity of 600 MTPD

More capacity with three COPE trains than four air-based trains!

Normal operating mode would be operation in COPE Phase I mode

Switch quickly to COPE Phase II operation on both operating

trains if one train goes down, still providing 1200 MTPD capacity

Configuration SRU Capacity (TPD)

Train 1 Train 2 Train 3 Train 4 Total Total - with one train down

Air-Based 400 400 400 400 1600 1200

COPE Phase I 400 400 400 None 1200 Switch to COPE II

COPE Phase II 600 600 600 None 1800 1200

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Four 400 TPD air-

based SRUs &

TGCUs

Three 300 TPD air-based

SRUs & TGCUs

+ ASU for O2 (and N2)

Capital Cost Base Base - $ 70 MM*

Yearly Operating Cost

Power (5c/kwh) Base Base + $0.7 MM

Natural Gas

($4/MSCFH)

Base Base - $1.3 MM

Emissions (tonnes/year)

SO2 Base Base - 59.7

CO2 Base Base - 23,500

Air-based vs Grassroots COPE

Capital, Operating Cost, Emissions Comparison

SUBSTITUTE AN ASU FOR A SRU !!

* +/- 25% USGC basis

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Summary

An SRU configuration utilising the COPE technology provides:

Very significant capital savings estimated at US $ 70 million

Operating cost savings or cost neutral

Reductions in CO2 emissions

Reductions in SO2 emissions

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Oxygen Supply Options

Liquid Oxygen Supply via on-road liquid oxygen tankers from central manufacturing facilities

On-site production

– Cryogenic Technologies (co-product N2)

– Adsorption Technologies

Pipeline Supply

An on-site ASU can achieve further economies of scale by supplying oxygen to other potential applications such as the FCC and also supplying the N2 needs of the refinery and other potential users in the vicinity

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Conclusions

Hydrogen supply and sulfur recovery are inextricably linked and of growing importance for the modern complex refinery

Ongoing technological advancements in H2 manufacture have helped significantly improve energy efficiency and lower the CO2 footprint

A hydroprocessing expansion or a new refinery can realise large capital savings via over-the-fence H2 supply and oxygen-based SRUs.

Oxygen-based SRUs can significantly reduce CO2 and SO2 emissions

Implementation of the COPE technology for grassroots refinery or gas plant SRUs provides large capital savings even after accounting for the costs of a dedicated ASU

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