Maarten Mys PolysepTM Membrane Systems

Honeywell UOP Enhancing Hydrogen Recovery

March 6-7 2017 UOP India Refining and Petrochemicals Technology Conference
Delhi, India
UOP 7804I-0 2017 UOP LLC. A Honeywell Company All rights reserved.
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Presentation Outline

Process Basics
Membrane applications
Supply model
UOP experience
Integration with PSA
Integration with UOP licensed technology
Q&A

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H2 Purification PolysepTM Membrane Systems

Non-Permeate
High Pressure
P 1.5 bar

FEED GAS

H2 + Impurities
High Pressure

Permeate
High Purity H2
H2 Purity 90 95 % Low Pressure
H2 Recovery 70 98 %
H2 Feed pressure 15-180 bar g
H2 Product pressure 5-80 bar g
All streams at constant flow, pressure, and temperature

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PolysepTM Membrane Technology

Driving Force =
A pressure differential across the membrane

High Pressure M
P
(Feed) e Qx = A p x
m t
b H2
H2 r Permeability (P) for different components
a Relative permeability: selectivity ()
n Low Pressure
Permeability and selectivity are strongly T-dependent
e (Permeate)
Membrane design parameters : thickness (t), area (A)

H2O, H2, He
Soluble in membrane
Fastest Small molecule
M
FAST e
m
SLOW b H2S, CO2,
r O2
a
n CO, CH4, N2, Ar, C2+
e Insoluble in membrane
Slowest
Large molecule

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PolysepTM Membrane Cartridges

Composite membrane Feed Inlet

Two or more polymers Permeate Permeate

Outlet Outlet
Thin and highly optimized
polymer for separation
Thicker polymer used for
increased strength and durability Non-Permeate
Outlet

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PolysepTM Membrane - Applications

Example: H2 Purification Example: CO Production
Carbon
Non-Permeate Monoxide
Refinery Off-Gas To Fuel or further Partial Oxidation 95 - 99% Purity
Methanol Off-Gas upgrading or Steam Reformer 95% Recovery
Ammonia Plants + CO2 Removal

15 - 180 bar(g) 18 - 35 bar(g)

50 - 80C 30 - 45C
200 - 100,000 Nm3/hr Hydrogen 50 - 70% CO
Hydrogen
20 - 95% H2
5 - 88 bar(g) 90% Purity
70 - 98% H2

Example: Synthesis Gas Ratio Adjustment

Synthesis Gas
Partial Oxidation or H2:CO = 1:1
Steam Reformer +
CO2 Removal

H2:CO = 2:1 - 3:1

CO2 < 100 ppmv
H2 + CO
To Fuel or further
Upgrading

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PolySEPTM Membrane System UOP Supply

Skid-mounted unit
1 or more Module and / or Pretreatment skids
Membrane cartridges delivered seperately
Very small to ultra-large systems
Modular supply:
Fully prefabricated
Plug and play concept
Minimal field work
B.L. connections
JB connections
Few to no field welds
Highest quality standards
Shorter delivery time

Exceptional UOP technology delivered fast and with the highest quality
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PolySEPTM Experience Modular Design

Small systems
Large systems
Limited plot space compact design
PSA/Membrane Integration

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PolysepTM Membrane UOP Experience

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PolysepTM Membrane UOP Experience Continued

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PolysepTM Membrane UOP Reference List

Largest Feed First Plane

Feed Source H2 in Feed (%) Rate Nm3/H On Stream No. Units
Steam Reformer 50-72 26,903 1992 6
Refinery Streams* 20-92 114,849 1985 47
Ethylene Off-Gas 78-80 5,749 1996 2
Methanol Off-Gas 60-79 80,040 1992 2
Ammonia Off-Gas 66-74 46,000 1992 4
Partial Oxidation** 42-75 550,777 1987 15
Misc. Off-Gas 29-89 27,900 1988 6
Confidential 12-99 15,628 1986 3
Total Units 84

* includes Hydrotreating/Hydrocracking
** includes Oxo-alcohols, syngas and IGCC

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H2 Recovery and Purification Technologies

Pressure Swing Permeation Cryogenic
Adsorption (PSA) Membrane Separation

Very High purity High purity High purity

99.8+% on-stream Up to 95% recovery By-products
reliability factor Low Pressure H2 High pressure H2
Up to 90% recovery Non-permeate to fuels CAPEX & OPEX
High Pressure H2 Needs pre-treatment
Tail gas to SR burners
Operational Flexibility

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PolybedTM PSA & PolysepTM Membrane Integration

UOP has delivered the largest PSA and Membrane systems in the world
UOP has the unique capability to study the combination of both
seperation technologies to maximize performance
In order to improve hydrogen recovery multiple combinations are
possible:
If the PSA comes first, tail gas can be sent to a membrane for
further upgrading
If the membrane comes first:
Permeate could be sent to a PSA for further upgrading
Non-permeate could be sent to a PSA for further upgrading
Different purity needs
Different pressure level constraints
Combined PSA and membrane systems can achieve H2 recoveries
up to 99%
On certain applications, H2 recovery of 100% can be achieved

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PolybedTM PSA & PolysepTM Membrane Integration

Conventional Integrated
PSA Recycle PSA PSA/Membrane
Design Hydrogen Recovery 90% 95% 98%

Design Hydrogen Produced, Nm3/h 100,000 105,000 108,000

Incremental Hydrogen produced, $/yr -- ~ $5.0 MM/yr ~ $8 MM/yr

Incremental Fuel Gas lost, $/yr (1) -- (~ $1.5 MM/yr) (~ $2.2 MM/yr)

Incremental Additional CAPEX -- 37% 60%

Incremental OPEX
-- $1.1 MM/yr $0.5 MM/yr
(Compression Power)

Payback, relative to conventional -- <11 months <8 months

SMR CAPEX Savings -- ~ 5 MM ~ 8 MM

UOPs expertise will optimize recovery for every situation

 H2 Purification Integrated in UOP Licensed 14

Technologies Platforming Case Study

UOP Platforming process is a large H2 source for a refinery

Traditionally a PSA unit will upgrade the off-gas to pure H2,
tail gas is sent to fuel
However tail gas still contains valuable hydrocarbons
A Platforming unit typically has a hydrocarbon recovery section
which can be fed by part of the PSA tail gas
Hydrocarbon recovery is however limited by feed quality
(hydrocarbon concentration) and chilling duty
A simple recycle of part of the PSA tail gas will improve the
hydrogen recovery

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Platforming Case Study Once Through System

Hydrogen
H2 Purity 99.9 %
H2 Recovery 88 %

Net Gas
Recontact
Section

Tail Gas

LPG Reformate

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Platforming Case Study Standard Recycle

Hydrogen
H2 Purity 99.9 %
H2 Recovery 94 %

Net Gas
Recontact
Section

Tail Gas

LPG Reformate

Recycle

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Technologies Platforming Case Study

UOP PolysepTM membranes are a unique add-on to this

setup improving both H2 recovery and the quality of the gas to
the hydrocarbon recovery section
Hydrogen recovery boosted from 87% to 98%
C3 & C4 recovery boosted from 45% to 89%
Lower fuel gas production
Lower energy consumption on chillers in Hydrocarbon Recovery Section
Lower capex of the Hydrocarbon Recovery Section
Depending on local economics, UOP can extend its
hydrocarbon processing technology with:
A PSA unit
A Membrane unit
Any combination of Membrane & PSA
To:
Maximize Hydrogen recovery
Maximize LPG recovery
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 Platforming Case Study Improved Recycle 18

for Maximized H2 Recovery

Hydrogen
H2 Purity 99.9 %
H2 Recovery 98 %

Net Gas Recontact

Section

Tail Gas

LPG Reformate

Recycle

Fuel Gas

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for Maximized H2 and LPG Recovery

Hydrogen
H2 Purity 99.9 %
H2 Recovery 98 %

Net Gas Recontact

Section

Tail Gas
Recovery
Max
Non-permeate

LPG Reformate
Recycle

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 Product Recovery Comparison 20

TG Recycle + Enhanced LPG Recovery

New Design: PSA Integration with Membrane Recycle + Recovery Max

Value (MM$/yr)
Recov
Base Max Delta [USGC] [NEA] [ME] [India]
LPG (C3+C4), KMTA 89 174 85 55.8 71.0 67.5 58.0
Recovery (LPG Product), Wt-% 45.3 88.5 --- --- --- --- ---
Reformate, KMTA 2483 2489 6 6.3 6.6 6.4 5.8
H2, KMTA 96 105 9 10.0 24.1 4.8 23.0
Recovery (PSA Product), % 89.0 97.7 --- --- --- --- ---
Fuel Gas, KMTA 211 113 -98 -28.5 -76.2 -8.7 -60.3
Net Product Value 43.5 25.5 70.0 26.5

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Evaluation Summary 21

TG Recycle + Enhanced LPG Recovery

All Region
USGC NEA ME India
CAPEX Investment (EEC*), MM$ 15.2

Equipment Investment, MM$ 5.1

Delta Operating Margin, MM$/yr 40.8 17.9 68.6 24.0

Product Value Increase, MM$/yr 43.5 25.5 70.0 26.5
Utility Savings, MM$/yr -2.8 -7.6 -1.4 -2.5

Delta 10 yr NPV (10% rate of return), MM$ 235.2 94.5 406.0 132.2

* EEC factor = 3

Increase H2 and LPG recovery Reduce your SMR size

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