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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
3
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
4
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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Tell me more… www.airproducts.com
morrisp3@airproducts.com
Thank you
Q&A
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