1914 - 2014 A Century of Innovation in the Oil and Gas Industry
© 2014 UOP LLC. All rights reserved.
Evaluation of Hydrogen Production at Refineries in China
The new UOP SeparALLTM Process
Bart Beuckels, UOP NV
IChemE Gasification Conference March 12, 2014 Rotterdam, the Netherlands
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UOP Company Profile Serving the Gas Processing, Refining & Petrochemical Industries
Profile — Significant Technology Position
Business Units: Gas Processing and Hydrogen (GP&H)
Process Technology & Equipment (PT&E)
Catalysts, Adsorbents & Specialties (CA&S)
Renewable Energy and Chemicals (RE&C)
Offering: Technology, catalyst & services to the refining,
petrochemical and gas processing industries
Supplier of molecular sieve adsorbents to process and manufacturing industries
UOP Facilities — Global Footprint Sales: Geographic
Sales: Breakdown
North
America
32%
Asia Pacific
19%
China
12%
Middle East
9%
South
America
9%
E&A 9%
CIS 5%India
5%
UOP Offices
UOP Manufacturing Sites
20 Offices
17 Countries
12 Manufacturing Facilities
5 Engineering Centers
Worldwide Headquarters Des Plaines, Illinois (suburban Chicago)
3,500+ Employees
Global
Customers
Equipment
45%
Licensing
7%
Services
13%
Products
35%Equipment
Products
Services
Licensing
UOP 6196-2
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Benefits of a UOP Integrated Solution in a Refinery
Our technologies and products are designed to deliver superior performance, safety and value when combined in an integrated system:
High availability and reliability of processes and products
Lower capital expenditure and operating costs resulting in lower cost of production of hydrogen
Acid Gas Removal PSA Sulfur Recovery
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Growth Potential for Hydrogen
9.3 9.9 9.6 9.8 10.2 10.9 12.0 12.6
2.9 3.6 4.0 4.3
4.9
7.6
10.0
11.2
1.1
1.1 1.6
2.0
2.6
2.8
4.5
5.4
0
5
10
15
20
25
30
2008 2009 2010 2011 2012 2015 2020 2022
Mil
lio
n T
on
s
Years
Methanol
Refineries
Ammonia
21
26
29
18
16 15
15
13
Source: Chem1 Market Assessment Study for Hydrogen
Growth for hydrogen will mainly come from the oil refining industry
Hydrogen segment assessment in China (Million tons) CAGR 2012-2022
8%
8%
2%
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Five Year Plan Target … Control Sulfur Emissions
Increasing sour crude processing and stricter sulfur
controls requires added capacity for hydrogen production
Fuel Standards State II
Current
State III
2013
State IV
2015
State V
GASOLINE Sulfur, ppm
Olefin, v%
Manganese, g/L
Vapor pressure
(Summer), kappa
500
35
0.018
74
150 30
0.016
72
50 28
0.008
40~68
10 25
0.002
40~65
DIESEL Sulfur, ppm
Cetane number
Density, 20℃ kg/cm3
Fatty acid ester
Heavy Aromatics
500 49
820-860
/,/
350 49
810-850
0.5%v,11%m
50 51
820-845
/, 11%m
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Source: Chem1 Market Assessment Study for Hydrogen; Hart Energy Consulting Analysis (2010)
DIESEL
Comments
Improving energy efficiency combined with reducing
greenhouse gas emissions are key in the five year plan
China relies heavily
on the ME for most
of its oil supplies
which is sour
ME Crude Oil Specs:
Current
API = 34
S (wt%) = 1.75
API = 33.9
S (wt%) = 1.84
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Breakdown of Feedstock for Hydrogen Production
Coal gaining prominence as an alternative cheaper feedstock
1.1 1.2 1.3 1.4 1.5 1.7
1.9 2.1
0.6 0.7
0.8 0.8
0.9
1.1
1.9
2.1
0.1 0.1
0.1 0.1
0.1
0.6
0.6
0.8
0
1
2
3
4
5
6
2008 2009 2010 2011 2012 2015 2020 2022
Mil
lio
n T
on
s
Year
others
coal
NG
ROG
Source: Chem1 Market Assessment Study for Hydrogen
Hydrogen market assessment in China (Million tons)
1.8
2.0 2.2
2.4 2.5
3.4
4.4
5.0
18%
9%
4%
CAGR 2012-2022
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Case Study Comparing SMR & Gasification
1. Basis
Natural Gas Price: $13/MMBtu (HHV = 22,400 Btu/lb) - based on LNG imports
Petcoke Price: $1/MMBtu (HHV = 15,000 Btu/lb)
Coal Price: $3.50/MMBtu (HHV = 12,000 Btu/lb)
Hydrogen required for refinery: 100,000 Nm3/h
2. Configurations
H2
CO2
H2S
Desulfurization
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Petcoke
Coal
O2
ASU
Pure H2 To
Refinery
Syngas
Natural
Gas/ROG
Gasification
Pure H2 To
Refinery
Polybed PSA
Polybed PSA
SMR
CO Shift UOP
SeparALL
Process
H2
CO Shift
UOP 6196-7
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Hydrogen Production Cost
0.212
0.153
0.110
Natural gas Coal Petcoke
Hydrogen production cost in China, $/Nm3
UOP processes drive value in hydrogen production
Cheaper feedstock cost directly influences
the cost of hydrogen production
1.01 1.67
0.10 0.11 0.12 0.13 0.14
Capex $ MM
Feedstock $/MMBTU
SENSITIVITY ANALYSIS FOR PETCOKE FEED
11.89 14.11
0.18 0.19 0.20 0.21 0.22 0.23 0.24
Feedstock, $/MMBTU
Capex $MM
SENSITIVITY ANALYSIS FOR NATURAL GAS FEED
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What is the new UOP SeparALL Process?
Absorption / regeneration process for selective removal of H2S, COS, & CO2
Uses “Next generation” physical solvent (SELEXOL™ MAX Solvent)
– Chemically similar and completely compatible with SELEXOL Solvent
– Clear fluid that looks like tinted water
Solvent regenerated by changing pressure, temperature or applying a stripping gas
Physical vs Chemical Typical Gasification Application
High Pressure is advantageous
So
lve
nt L
oa
din
g
Physical Solvent
Chemical Solvent
Partial Pressure
UOP 6196-9
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Two Basic Flow Schemes
Sulfur removal only
Typically for power and hydrogen applications
Can reduce treated gas any desired sulfur level
One solvent absorber with solvent regeneration
Sulfur removal with separate CO2 removal (CCS or chemicals production)
Typically for chemicals, SNG or coal to liquids applications
Typically involves more stringent product specifications
Integrated solvent absorbers and solvent regeneration
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UOP SeparALL Process - Advantages
Solvent: high vapor pressure (low losses) and non-toxic
Mild Chilling
Simple flow schemes with few pieces of equipment
Absorbs NH3, HCN and other trace contaminants, without the need for additional equipment
Removes metal carbonyls
Metal carbonyls in treated syngas decompose at gas turbine burners and potentially plate-out on the gas turbine blades
Metal carbonyl can also act as catalyst poisons for chemical applications
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Through its improved efficiency and next generation
technology, the SeparALL process can reduce capital
expenditures by up to 10 percent and operating
expenditures by more than 20 percent.
UOP 6196-11
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Commercial Experience in Hydrogen Production
ITALY
Sarlux IGCC CLICK TO LEARN MORE
U.S.
Coffeyville
Resources CLICK TO LEARN MORE
UOP 6196-12
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Sarlux IGCC Complex Plantt
Start-Up 2000
Application Power H2 Production
Production 550 MW net / 40000 Nm³/h
AGRU Duty Sulfur
Syngas Flow 404 MMSCFD @420 psia
Feedstock Visbreaker Residue
Commercial Experience in Gasification
Sarroch, Sardinia, Italy
Sarlux IGCC Complex Plant
UOP 6196-13
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Electric Power
Raw
Elemental Sulfur
Steam for Export
High Purity to Hydrocracker
PolybedTM
PSA
PolysepTM Membrane
Combined Cycle Power
Plant
Claus Plant SELEXOL Gas Cooling
& COS Hydrolysis
Air Separation
Unit
Gasifier w/ Quench
& Scrubbing
H2
Feed
Tail Gas
Air
O2
H2
Block Flow Diagram | Sarlux IGCC
Purified Syngas
UOP 6196-14
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Coffeyville Resources Plant
Start-Up 2000
Application Ammonia Urea
Production 21 T/h | 62 T/h
AGRU Duty Sulfur & CO2
Syngas Flow 151 MMSCFD @535 psia
Feedstock Petcoke Coffeyville, Kansas
Coffeyville Resources Plant
Commercial Experience in Gasification
UOP 6196-15
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Acid Gas
Ammonia Synthesis
Claus Plant
Syngas Scrubbing
Quench Gasification
Air
N2
UAN Plant
NH3 Product
UAN Product
Block Flow Diagram | Coffeyville Resources
Air Separation
Unit
Petroleum Coke
CO Shift & Gas Cooling
Raw CO2
CO2
Vent CO2
Purification
SELEXOL 2-Stage
Purified CO2
Polybed PSA
Tail Gas
High Purity H2
Raw H2
O2
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UOP Polybed PSA Systems
H2 @ High Purity High Pressure
Impurities (+H2) Low Pressure
H2 + Impurities High Pressure
H2 Purity 99.9 – 99.9999%
H2 Recovery 60 – 90%
H2 Feed pressure 6 - 40 bar g
H2 Product pressure 5 - 39 bar g
PRODUCT
FEED GAS
TAIL GAS
UOP 6196-17
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10-bed 47000
12-bed 71000
Fast cycle 12-bed 113000
First 16-bed 223000
New Adsorbents
14-bed 253000
14-bed 100000
12-bed 150000
Optimized Adsorbents
Optimized Cycles
Methanator Replacement
Increased H2 demands
4-bed
High Purity H2
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UOP’s History in PSA Systems
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>1,000 Polybed PSA Units
UOP is the World Leader in PSA technology UOP 6196-19
Refinery Streams
23%
Ethylene Off-Gas
16%
Specialty Applications
19% • Ammonia Plants
• Coke Oven Gas
• Gasification
• Methanol Off-Gas
• Styrene Off-Gas
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Steam Reformers
42%
Applications of UOP’s Polybed PSA Systems
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Components of UOP Polybed PSA Systems
Control System
Valve Skid
Vessels & Adsorbents
UOP Service & Support
1
1
2
3
4
2
3
4
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PSA with Maximum On-Stream Reliability
For a customer in China that needs a reliable source of
high purity hydrogen, UOP Polybed™ PSA provides greater
than 99.8% on-stream availability that results in $500,000/day
of additional value due to downtime avoided versus local
PSA suppliers. We do this by providing proven designs,
proprietary adsorbents, and equipment.
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Assumptions:
• 100,000 Nm3/hour product PSA unit
• H2 value = 15000 RMB/MT = $0.21/Nm3
• Calculation: 100,000 x 24 x 0.21 = $504,000/day
• The cost from the loss of production from the
downstream hydroprocessing units, if known,
would be added to the cost of the loss of H2
UOP 6196-21
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Q u e s t i o n a n d A n s w e r
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1914 - 2014 | A Century of Innovation in the Oil & Gas Industry
