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

Phil Morris and Uday N. Parekh , Air Products Elmo Nasato Goar, Allison & Associates, Inc
Middle East Downstream Week Abu Dhabi, 8-11 May 2011

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

Light / Sweet Crude Heavy / Sour Crude

H2

Hydrorefining
Low conversion refinery
Transportation fuel 42% Other 24% Residual fuel 34% H2 Nm3/m3 0 25 Sulphur spec. > 1000 ppm
4

High conversion refinery

Transportation fuel 82% Other 17% Residual fuel 1% H2 Nm3/m3 700 1000+ Sulphur spec. <30 to <10ppm

Air Products & Technip: #1 Suppliers to the Refining Industry

Tonnage Hydrogen

Air Products 2,556 kNm3/hr ~43%

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

On-stream 2010 - 5,945 kNm3/hr

www.h2alliance.com

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 prereforming technology with more than 40 units to Technips credit Air Products was the first industrial gas company to apply it in a large hydrogen plant on multiple feedstocks

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

Port Arthur II Integrated SMR/Cogen

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Hydrogen Technology Map

Advanced cycle CO2 management

H2 Technologies Progression

Advanced ROG integ. Exten. Pre-reforming Enhanced SMR severity Higher severity SMR pre-reforming - MTS Advanced heat recovery SMR full GTE-HRSG RFG integration Max power /steam Multi feed Pre-reforming High severity SMR SMR Cogen GTE integration Pre-reforming APH SMR no APH HTS PSA ROG feed mix

1994
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Timeline

2012

Hydrogen Plant Efficiency Improvement Over Two Decades

Relative H2 Plant Feed & Fuel % 102 100 98 96 94 92 90

88

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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 refinerys 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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Clean Fuels and High Conversion

Clean Fuels H2
Intensive Hydro processing O2 H2S

An Inconvenient AGR / SRU Consequence !!

Clean Sulfur
Degassing

On to sulfur recovery >>>>>>

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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 DGAASSTM 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

Nitrogen bottlenecks the SRU !!

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Why Oxygen Enrichment Increases SRU Capacity

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 20.9 (air) 100 50 189 339 293 25 113 57 169 339 286
50 170 85 84 339 261

100 226 113 0 339 235

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Total flow constant; Acid gas flow increases as O2% increases

SRU Capacity Increase with O2 Enrichment Three Proven Technologies

180 Acid Gas Concentration 92% H2S

160
% Capacity Increase

Low Level Enrichment COPE Phase I

140
120 100 80

COPE Phase II

70% H2S 50% H2S

60 40
20 0 20 30 40 50 60 70 % Oxygen 80 90

35% H2S

100

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PROCESS GAS

COPE PHASE II PROCESS

MOTIVE STEAM EJECTOR

RECYCLE GAS

COMBUSTION AIR

Recycle stream added to control RF temperature Enrichment up to 100% O2 NATURAL GAS

Capacity up to 250% of air based capacity

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COPE 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
SRU Capacity Increase with Oxygen Enrichment
180 % Capacity Increase 160 140 120 100 80 60 40 20 0 20 30 40 50 60 70 80 90 100 Mol % Equivalent Oxygen 50% H2 S 35% H2 S Low Level Enrichment COPETM Phase I COPETM Phase II 70% H2 S 92% H2 S*

TM

Experience Commercialised in 1985; 25 years of reliable, continuous operation > 30 units in operation
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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) Contained S in Feed, TPD SRU Tail Gas Flow, Nm /h Contained S in Tail Gas, TPD Feed Gas to TGCU Amine 3 Absorber, Nm /h
3

Air-Based Operation 100 TPD 100 9,456 2.7 6,885

COPE Operation COPE vs (65% O2) Air-Based 200 TPD 200 8,625 4.2 2,786 % Increase 100% -9% 56% -60% Feed to absorber 60% lower despite 2X capacity Feed to incinerator 62% lower despite 2X capacity Comments

Absorber Off-Gas to Incinerator, 3 Nm /h

H2S Level in Absorber Off-Gas, ppmv Contained S in Gas to Incinerator, kg/hr SO2 Emissions from Incinerator Stack, TPY
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6,830

2,625

-62%

80

80

0%

0.78

0.30

-62%
SO2 emissions 62% lower despite 2X capacity!

13.68

5.26

-62%

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

Crude properties: 21.9 API, 0.92 spec gravity, 3.3 wt% sulfur Sulfur plant/s capacity: 500 TPD New Capacity or Expansion (bpd) Naphtha HDS Kerosene HDS Diesel HDS

VGO HDS Hydrocracker

Sulfur Generated (TPD) 10,000 20,000

30,000 40,000 50,000 60,000 70,000

2.5 5
7.5 10 12 15 17

10 20
30 40 50 60 70

27 54
81 107 134 161 188

41 81
122 163 204 244 285

48 94
142 189 236 283 330

Legend: Oxygen Enrichment Technologies Low-Level Mid- Level -- COPE Phase I High - Level -- COPE Phase II
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up to 25% SRU Capacity Increase up to 45% SRU Capacity Increase up to 120% SRU Capacity Increase

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
Configuration Train 1 Air-Based COPE Phase I COPE Phase II 400 400 600 Train 2 400 400 600 Train 3 400 400 600 SRU Capacity (TPD) Train 4 400 None None Total 1600 1200 1800 Total - with one train down 1200 Switch to COPE II 1200

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

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Air-based vs Grassroots COPE Capital, Operating Cost, Emissions Comparison

Four 400 TPD airbased SRUs & TGCUs Three 300 TPD air-based SRUs & TGCUs + ASU for O2 (and N2)

Capital Cost Yearly Operating Cost Power (5c/kwh) Natural Gas ($4/MSCFH) Emissions (tonnes/year) SO2 CO2
* +/- 25% USGC basis

Base

Base - $ 70 MM*

Base Base

Base + $0.7 MM Base - $1.3 MM

Base Base

Base - 59.7 Base - 23,500

SUBSTITUTE AN ASU FOR A SRU !!

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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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Thank you
Tell me more
www.airproducts.com morrisp3@airproducts.com

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Q&A