CO2 CAPTURE

Cryocap™ is a technological innovation for CO₂ capture using

a cryogenic process involving low temperatures, around -50°C,
combined with membranes separation, that is unique in the world.
It can be adapted to specific applications combining a variety
of Air Liquide technologies: the capture of CO₂ produced
by thermal power plants (Cryocap™ Oxy), or hydrogen production
units (Cryocap™ H₂).

22 Air Liquide Engineering & Construction Technology Handbook

Overview

H2 or Syngas
Hydrogen
& Syngas Cryocap™ H2 #24
Generation
CO2 for CCS

Carbon-free Flue Gas

Oxycombustion Cryocap™ Oxy #25

CO2 for CCS

Technology Handbook Air Liquide Engineering & Construction 23

 CO2 CAPTURE Cryocap™ H2 – Cryogenic CO2 Separation

Application Description H2 Product

CO₂ capture from

The offgas is compressed, dried and sent Natural SMR Schift H2 - PSA
H₂ production plants gas
to a cryogenic unit, where the CO₂ is separated
Feedstock from the other components by a combination of
partial condensation and distillation. A pure and Fuel
Offgas from H₂ plant Cryocap™ H2
pressurized CO₂ flow is produced from the cold
Product box.
CO₂ The non condensed gases are recycled through Membranes
a membrane system to recover H₂ and CO₂.
Co-product Residual gas is sent to the burners of the
H₂ reformer.

Capacity The CO₂ product is compressed up to

Cold Co2 Product
supercritical pressure or liquefied and stored Box
From 500 to 2,000 tpd
in liquid storage.
Economics Food-grade quality can be achieved by
Opex + Capex: an additional purification on a catalytic bed Residue
- 45 USD/tonne of CO₂ where all remaining hydrocarbons and alcohols to fuel gas
are destroyed.
- Increase H₂ production
by 13% to 20% Cryocap™ H₂ can be installed for greenfield as
well as brownfield H₂ plants.
- Cryocap™ H₂ offers the lowest costs
for CO₂ production from H₂ plant Main feature:
(20% less capex than amines) • More than 98% of CO₂ recovery from syngas

Reference
1 (100 000 t/y)

Contact
cryocap@airliquide.com

24 Air Liquide Engineering & Construction Technology Handbook

 CO2 CAPTURE Cryocap™ Oxy – Cryogenic CO2 Separation
for Oxycombustion

Application Description
Non condensable
CO₂ capture from power plants to vent
The flue gas issued from the boiler plant is first
Feedstock treated in a pre-treatment unit, which aims to cool
the gas and remove the SOx, HF, HCl, most of the
Oxycombustion flue gas
NOx, and the dust. Then the gas is compressed
Flue Gas
Product and dried before entering the cryogenic
CO₂ purification unit.
Cold Box
In the cold box, CO₂ is recovered by combination Low Pressure
Co-product of partial condensation and distillations, which Pre-Treatment
None allow the removal of the heavy compounds such
as NOx and the light elements such as O₂, Ar, N₂,
Capacity NO and CO.
CO₂ Product
From 1,000 to 15,000 tpd
The CO₂ product is compressed, condensed
Economics and pumped up to supercritical pressure.
Cryocap™ Oxy allows very high CO₂ Main feature:
recovery and near zero-emission to • More than 98% of CO₂ recovery from syngas
the atmosphere (SOx, particulate matters,
NOx, Hg). References
Capex: 40 to 300 mm USD
3 (from 25 000 to 1.2 million t/y)

Contact
cryocap@airliquide.com

Technology Handbook Air Liquide Engineering & Construction 25

 HYDROGEN & SYNGAS
GENERATION
We are pushing technology limits in design and delivery of syngas
plants, including the world’s largest units. Our plants meet the needs
of large, medium, and small customers with a wide range of possible
steam export rates.

26 Air Liquide Engineering & Construction Technology Handbook

Overview

Steam Methane #28

Reformer #29 #30

Natural gas
Autothermal #31
LPG Reformer
Naphtha
CO2
Capture
Gas POX #32

Chemicals

Liquid residue Hydrogen

Lurgi MPG™ #33 & Syngas
from oil refining
Separation
Rectisol #35

Coal Lurgi FBDB™ #34

Technology Handbook Air Liquide Engineering & Construction 27

 HYDROGEN
& SYNGAS
GENERATION
Application
Generation of syngas by steam reformation
of methane rich hydrocarbon
Feedstock
LPG, naphtha, natural gas, refinery off-gas
Product
Hydrogen, carbon monoxide,
syngas or a combination thereof
Co-product
Steam, optionally carbon dioxide
Capacity
Per SMR train:
- 15,000 - to 200,000 Nm3/h H₂ plant
- 3,500 - 40,000 Nm3/h CO plant
- Up to 350,000 Nm3/h syngas
Economics
Opex:
H₂ plants (based on nat. gas feed & fuel):
Steam co-export ratio: 0.4 to 1.1 kg/Nm3 H₂
Feed+Fuel: 14.5 to 15.3 MJ/Nm3 H₂
HyCO plants (based on nat. gas feed & fuel):
H₂/CO product ratio: 2.6 to 4.2
Steam co-export ratio: 0.3 to 0.7 kg/Nm3
[H₂+CO]
Feed+Fuel: 14.2 to 14.8 MJ/Nm [H₂+CO]
3
Capex:
H₂ and HyCO plants (incl. purification):
25 to 370 mm USD
28 Air Liquide Engineering & Construction Technology Handbook
Steam Methane Reforming (SMR)
Flue Gas HP Steam
Description
Feedstocks are desulfurized, mixed with steam
Process Steam Heat
and pre-heated. Recovery
Flue Gas
Optionally a catalytic pre-reforming step may be Fuel Gas
foreseen to convert the feed/steam mixture to a Tail Gas
methane rich gas to improve efficiency of the
SMR.
The main reforming reaction takes place in the Natural Pre- Syngas
Gas Reformer
proprietary top-fired steam reformer in which the
Syngas
feed/steam mixture is converted while passing Reformer Cooling
Hydro-
catalyst filled and heated tubes at temperatures H2 desulfurization
Pre-Treatment Boiler Feed
of 800 to 940 °C and pressures of 15 to 45 barg. Water
Reformed gas leaving the reformer contains H₂,
CO, CO₂ and unreacted components.
Efficiency of the process and composition of the
reformed gas can be adjusted via the process Main features:
parameters reforming pressure, temperature and • Flexibility in process design to optimize
steam to feed ratio. for best efficiency, lowest Capex or lowest total
cost of ownership
In case H₂ yield should be increased or
maximized a catalytic shift reactor may be added • Optimized integration of refinery off-gases
and fed with reformed gas to convert CO and for H₂ production and recovery
steam to additional H₂ and CO₂. • Best in class plant reliability and operability
through operational feedback from Air Liquide’s
In case a high CO yield is targeted CO₂ may be
own plants.
separated from reformed gas and recycled to the
SMR. Additional import CO₂ may be added if References
available.
> 140 (> 40 in last 20 years)
Suitable product purification technologies
include: PSA and membrane for H₂, amine wash Contact
(aMDEA) for CO₂ removal and methane wash
Cold Box for CO. hydrogen-syngas@airliquide.com
 HYDROGEN
& SYNGAS Small-Scale Standard Hydrogen Plant
GENERATION

Flue Gas HP Steam

Application Description
Hydrogen production by steam reforming in
The small-scale standard H₂ plant product
a highly standardized and modularized plant Process Steam
is based on hydrogen production via steam Heat
Recovery
Feedstock reforming of hydrocarbon feedstocks. Flue Gas
Additionally a CO-shift and PSA unit are included Fuel Gas
Natural gas, refinery off-gas, Tail Gas
to maximize the H₂ yield and purify the H₂. For
LPG, naphtha
more details regarding the process technology
Product reference is made to the description of Steam
Hydrogen Methane Reforming (SMR). Natural H₂
Gas Co Shift Product
The small-scale standard H₂ plant product
Co-product includes four different plant sizes with pre- Hydro- Reformer
Steam defined equipment, piping arrangement and desulfurization
Boiler Feed PSA
Pre-Treatment
lay-out. Water
Capacity
Its design is optimized for minimum total Recycle
15,000 - to 45,000 Nm3/h H₂ Hydrogen
cost of ownership, but nevertheless allows for
Economics considerable process flexibility.
The product is suitable for receiving different
Opex:
types of feedstocks, its configuration may be
Feed+Fuel: 14.5 to 15.0 MJ/Nm3 H₂ (Figures
selected for high or low steam co-product ratios
based on nat. gas feed & fuel)
with an option for high export steam quality. A
Capex: pre-reformer may be included as well, particularly
25 to 60 mm USD in combination with liquid feedstocks.
Main features:
References
• Design of standard plant allows for considerable
process flexibility >20 (6 in last 10 years)
• High degree of modularization to limit exposure
during construction
Contact
• Compact plant layout and small foot-print hydrogen-syngas@airliquide.com
• Delivery time < 15 month FOB from project
award

Technology Handbook Air Liquide Engineering & Construction 29

 HYDROGEN
& SYNGAS SMR-X™ – Zero Steam Hydrogen Production
GENERATION

Application Description Flue Gas

Production of hydrogen in a radiative heat
SMR-X technology is based on a new generation
exchange steam methane reformer (SMR)
steam methane reformer furnace with additional
without co-export of steam Process Steam Heat
heat recovery of the reformed gas leaving the
Recovery
Feedstock reaction zone back to the catalyst bed. Flue Gas
To achieve this, the reformed gas passes Fuel Gas
Natural gas, refinery off-gas, Tail Gas
via heat exchange tubes, located inside the main
LPG, naphtha
reformer tubes, before leaving the reformer.
Product Geometry and material of the internal heat
Natural Pre- H₂
exchange system is optimized for high efficiency Co Shift
Hydrogen Gas Reformer SMR-X Product
and reliability. Consequently, utilization of SMR-X
Co-product allows for a H₂ plant design with balanced steam H₂ Hydro-
None (optionally steam at low co-export desulfurization
production and consumption at superior overall Pre-Treatment
Boiler Feed PSA
Water
ratio) process efficiency compared to conventional
SMR technology. Also, highly efficient H₂ plant
Capacity designs with very low steam co-export ratios are
Up to 100,000 Nm3/h hydrogen possible.
Economics Furthermore, the plant’s steam system is
simplified and the reformer size of SMR-X is
Opex:
reduced compared to a conventional furnace,
Feed+Fuel: Appr. 13.6 MJ/Nm3 H₂
because approximately 20% of the required
(Figures based on nat. gas feed & fuel)
process heat is supplied by internal heat
Capex: exchange.
25 to 135 mm USD
Main features: Contact
• H₂ plant de-coupled from steam host
hydrogen-syngas@airliquide.com
• Highest efficiency of all available zero steam
solutions
• >5% reduction of CO₂ emissions compared to
conventional SMR based zero steam design
• Attractive plant Capex due to compact reformer
design

30 Air Liquide Engineering & Construction Technology Handbook

 HYDROGEN
& SYNGAS ATR – Autothermal Reforming
GENERATION

Application
Production of syngas by partial oxidation of
gaseous hydrocarbon feed followed
by a catalytic reforming conversion.
The syngas can be used as feedstock for
different synthesis processes such as
methanol or Fischer-Tropsch synthesis.
Syngas components can be also separated
to pure products (H₂, CO, CO₂)
Feedstock
Natural gas, refinery offgas, pre- reformed
gas, Fischer-Tropsch tail-gas, LPG, Naphtha
Product
Syngas (H₂+CO)
Co-product
None
Capacity
Up to 1,000,000 Nm3/h
(dry) per reactor
Economics
Yield: 2.5- 4.0 Nm3 syngas / Nm3
natural gas (including fuel for fired heater)
Oxygen consumption:
0.15 - 0.25 kg O₂ / Nm3 syngas
Capex: 160 to 280 mm USD
Feed
Description
Desulfurized feed gas is preheated and Desulfurization
optionally pre-reformed prior to entering the ATR
reactor. The gas is fed via the proprietary burner
into a refractory lined reactor operating at 30 to
100 barg, where it reacts with oxygen and steam Fired Heater Steam
to form syngas. The syngas is further reformed
via a Ni-based catalyst bed located in the same
reactor. The syngas is cooled in a waste heat Pre-Reforming
boiler producing high pressure steam.
Depending on the needed syngas properties of
the downstream process this technology can be
ATR O₂
applied as stand-alone ATR or as a combination
of SMR and ATR known as Combined
Reforming.
Main Features: Heat Recovery Syngas
• Provide large quantities
of H₂-rich gas at lowest cost
• Compact reactor
• High pressure (up to 100 bar)
References
>30
Contact
hydrogen-syngas@airliquide.com

Technology Handbook Air Liquide Engineering & Construction 31

 HYDROGEN
& SYNGAS Gas POX – Natural Gas Partial Oxidation
GENERATION

Application Description Feedstock

Production of CO, oxogas and syngas by Feed gas is desulfurized, mixed with steam and
partial oxidation of hydrocarbon feed in a preheated in a fired heater.
Fired
refractory lined reactor Feed, steam and oxygen are fed from the HP Steam Heater /
HDS CO₂
proprietary burner to a refractory lined reactor
Feedstock
operating at up to 100 barg, where H₂, CO and
Natural gas, refinery offgas CO₂ are produced via partial oxidation.
Reformed gas is cooled down producing high PSA /
Product Gas
POX WHB
WHR / Gas
Cooling
Amine
Wash CO Coldbox Product
pressure steam. CO₂ is removed from the syngas O₂ Membrane
Syngas (H₂/CO < 1), oxogas,
in an amine wash unit.
carbon monoxide
In case a high CO yield is targeted CO₂ may be
Co-product separated from syngas and recycled to the POx.
Additional import CO₂ may be added if available.
Steam
Suitable product purification technologies
Capacity include: PSA and membrane for H₂, oxogas, ASU
Waste
Waster
Up to 150,000 Nm /h syngas
3 amine wash (aMDEA) for CO₂ removal and
partial condensation Cold Box for CO.
Economics Main Features: Air
Oxygen consumption: • Efficient technology for products with low
0.32 to 0.38 kg/Nm³ syngas (dry) H₂/CO ratio or for pure CO production
Capex: • Revamp of residue POx reactors allows
10 to 100 mm USD for switching to more economic nat. gas feed
• Low CO₂ footprint

References
6

Contact
hydrogen-syngas@airliquide.com

32 Air Liquide Engineering & Construction Technology Handbook

 HYDROGEN
& SYNGAS Lurgi MPG™ – Multi-Purpose Gasifier
GENERATION

Application Description Residue Value

Utilization of all kinds of liquid hydrocarbon

The feedstock together with oxygen and steam
residues from refinery or chemical Steam LP-Steam Pure CO₂ High BTU
is fed via the proprietary MPG-burner into the Low Sulfur
processes for the production of syngas by Fuel Gas
refractory lined entrained flow reactor operating
non-catalytic partial oxidation
at 30 to 100 barg, where it reacts in a non- Feedstock MPG™ Raw Gas Gas Rectisol™ PSA Hydrogen
Feedstock catalytic partial oxidation at typically 1,200 to (Quench) Shift Cooling
1500 °C to form syngas. The syngas leaving the
Typical feedstocks are residue from oil O₂ H₂S+CO₂
bottom of the reactor is cooled by quench or in a
refining like: asphalt, bitumen, tar, visbreaker Process Quench Sulfur
waste heat boiler, depending on feedstock
residue, hydrocracker residue, FCC residue, Water water O₂ OxyClaus™
characteristics and downstream usage. Claus Off-Gas
vacuum residue, coal tar, oil sand tar, etc
The proprietary MPG-burner design allows a
Product wide variety of feedstock properties to be Soot Water
ASU Filtration
Syngas (H₂ + CO) handled safely and reliably, covering high
viscosity and even occasional particles
Co-product up to millimeter size. The pressurized water Air Filter cake MPG based H₂ Production
None cooling of the burner insures safe operation
under all conditions. The technology may also be
Capacity adapted to the usage of slurries with solid
Up to 200,000 Nm3/h dry syngas content or bio-based syncrude. Contact
per gasifier
Main Features:
• Valorization of residues hydrogen-syngas@airliquide.com
Economics
capable of converting almost
Individual costs vary significantly depending
any liquid feedstock
on feedstock, size, location, integration in
• Highly tolerant to impurities
refinery, etc.
• High pressure
Oxygen consumption:
0 .7 Nm3 O₂/kg feed
Capex: 180 to 400 mm USD

Technology Handbook Air Liquide Engineering & Construction 33

 HYDROGEN
& SYNGAS Lurgi FBDB™ – Fixed Bed Dry Bottom
GENERATION
Coal Gasification
Application Description Sulphur
ASU Elemental Sulphur
Recovery Unit
Gasification of coal to produce syngas
Coal is converted into syngas by reacting in a
GOX FBDB
Feedstock counterflow fixed bed with oxygen and steam. CO₂ Rich Gas
The raw syngas will be further processed
Lumpy coal, especially suited for low-rank Coal
(CO-shift, Rectisol™) to meet the downstream FBDB™ (CO Shift) & Gas Syngas DRI Ammonia
(high ash, high water) coal Gasification Gas Cooling Purification SNG Liquid Fuel
requirements of the processes. Side streams are (Rectisol™)
HP Steam
Product further treated using proprietary technologies
to produce valuable co-products, as well as to Rectisol Naphtha
Syngas (H₂+CO), due to high CH₄ content Ash
particularly suited for the production of SNG meet environmental specifications. Special water
(synthetic natural gas) or DRI treatment allows for zero liquid discharge while
Gas Liquor Phenosolvan®
(direct reduction of iron ore) minimizing water consumption. Separation CLL™ ZLD / Water reuse
GLS Process™ WW Treatment
Main Features:
Co-product • Robust technology that can be fed with coarse
Liquid Ammonia

Crude tar acids (phenols), sulfur, lumps, avoiding the need for grinding and drying Phenols
tar, oil, naphtha, ammonia • Higher cold gas efficiency than entrained flow
Tar / Oil
gasification
Capacity • Wide variety of coal possible
40,000 to 120,000 Nm3/h dry syngas per • Lower water consumption than entrained
gasifier, typically more than 5 reactors per flow gasification
plant, largest plant 40 reactors at one site.
References
Economics
Individual costs depend strongly >100 gasifiers
on location, coal quality, etc. Contact
Yield:
2000 Nm3 dry syngas / ton dry coal hydrogen-syngas@airliquide.com
Capex:
420 to 650 mm USD
(cost base: 7 Mk+ in China)

34 Air Liquide Engineering & Construction Technology Handbook

 HYDROGEN
& SYNGAS Rectisol™ – Syngas Purification
GENERATION

Application Description Lurgi Rectisol® - The “5 in 1” Solution:

Feedstock Gasification 1 Trace contaminant removal
Selective removal of acid gases 2 Deep Desulfurization (total S < 80 ppb)
Acid gases in raw gases from any gasification are 3 Bulk CO2 removal (up to 100%)
(CO₂ and H₂S+COS) and of nearly all trace
removed by absorption with a physical solvent 4 CO2 purification (total S < 5 ppmv)
components (carbonyls, mercaptans, COS Dry CO2 Capture Ready (> 98.5 vol%)
(cold methanol). The rich solvent leaving the
HCN...) from syngas of any gasification (coal, Hydrolysys 5 Acid Gas Enrichment (S > 25 vol%)
contactor is regenerated by flashing and
petcoke, residue, heavy oil,...) to meet highest
stripping. Different process configurations are
specification reqirements for catalytic Trace
available to deliver a tailored solution optimized
processes. Removal
for Capex and Opex for a given syngas Acid gas suitable for
sulfur recovery processes
Feedstock specification.
Raw syngas deriving from gasification Rectisol™ is the leading process when it comes Sulfur Acid Gas H2S Sulfur
to the purification of gasification-based syngas Removal Enrichment CO2 Recovery
of any carbon containing feedstock
for catalytic applications (production of SNG,
Product methanol, ammonia, or Fischer-Tropsch) as well
Syngas suitable for
catalytic synthesis
Clean/high purity syngas (H₂+CO) as hydrogen processes CO2 CO2 CO2 CO2
Removal Treatment Compressor
for catalytic processes, clean hydrogen Using inexpensive solvent in combination with CO₂ suitable for
optimized heat integration, the Rectisol process compression, synthesis
Co-product or venting
has extremely low operating costs and high
H₂S rich gas for SRU, CO₂ offgas availability.
ready for storage/utililization
Main Features:
Capacity • Highest level of purity for all contaminants
100,000 to 1,000,000 Nm3/h per train • Low Capex and Opex when compared
to other purification process
Economics • Low cost solvent
Individual costs vary significantly depending • CO₂ offgas meeting most stringent emissions
on feedstock, size, purity request, etc. requirements References
Capex: 90 to 290 mm USD > 110 (> 35 since 2005)

Contact
hydrogen-syngas@airliquide.com

Technology Handbook Air Liquide Engineering & Construction 35

 HYDROGEN & SYNGAS
SEPARATION
Leveraging on our vast technology portfolio, we have the means
to combine various patented processes to address any Hydrogen
& Syngas separation challenge. Our customers benefit from
continuous improvements due to Air Liquide’s own track record
in its operational experience of such processes - from cryogenics
to permeation to adsorption.

36 Air Liquide Engineering & Construction Technology Handbook

Overview

Pressure Swing
Adsorption PSA #38
H2 Offgas
(Refineries, Pure H2
Crackers, PHD...)
H2 Membrane #42

Liquid Nitrogen
Wash #41 Ammonia Syngas (N2/H2)

Hydrogen Liquefier #43 Liquid Hydrogen

CO Cold Box #39 Pure CO

Methane Wash
Hydrogen
& Syngas
Generation CO Cold Box #40 Oxogas
Partial Condensation

Hydrogen

Technology Handbook Air Liquide Engineering & Construction 37

 HYDROGEN
& SYNGAS Pressure Swing Adsorption (PSA)
SEPARATION
Hydrogen Purification
PRODUCTION
Application Description
Recovery and purification of pure hydrogen
Pure H₂ product is delivered at a pressure close
from different H₂-rich streams
to feed pressure (pressure drop across PSA
Feedstock could be as low as 0.5 bar) and impurities are
removed at a lower pressure (typical PSA offgas
Raw hydrogen from SMR, POX, cryogenic
pressures range from 1.1 to 10 bara).
purification, methanol plant purge gases,
ethylene off-gas, styrene offgas, gasification, The PSA tail-gas, containing impurities, can be
ammonia plant, CCR, and other offgases or sent back to the fuel system (SMR burners
any combination of the above or refinery fuel network) with or without the need
of a tail-gas compressor. Operation is fully
Product automatic.
Hydrogen up to 99.9999% purity PSA units use the most advanced adsorbents
on the market and patented high efficiency
Co-product
cycles to provide maximum recovery and FEED OFF
None productivity. Typical on-stream factors are GAS
DRUM
Capacity >99.9%. OFF GAS

5,000 to 200,000 Nm /h 3 Turndown can be as low as 25%.

Economics
H₂ recovery rate: 60 to 90%
Opex: Feed+Fuel: Appr. 13.6 MJ/Nm3 H₂
(Figures based on nat. gas feed & fuel)
Capex: 1 to 5 mm USD
PSA units are compact, fully skid- mounted
and pre-tested units designed for outdoor and
unmanned operation.
References
>70 (in operation or under construction)

Contact
hydrogen-syngas@airliquide.com

38 Air Liquide Engineering & Construction Technology Handbook

 HYDROGEN
& SYNGAS CO Cold Box – Methane Wash
SEPARATION

Heat
Exchanger
Application Description
Carbon monoxide (CO) production Fuel
Methane Wash process is based on cryogenic H₂
or ratio-adjusted synthesis gas production COCH4
separation technology using the difference in Column
from synthesis gas for use in chemical
boiling points of the main components from the
industry
synthesis gas.
Wash Stripping
Feedstock Feed gas is pretreated to remove impurities Column Column

Synthesis gas from natural gas, naphtha or which will freeze at cryogenic temperatures
CH4
coal/residue. encountered in the process. It is then cooled Pumps
down in heat exchangers and washed with liquid
Product methane before being purified step by step
CO up to 99.99% purity through distillation columns.
Every cryogenic process is tailor-made to fit the
Co-product
customer’s specifications and other
Hydrogen, oxogas, methane, LNG requirements on co-products.
CO CO Expander
Capacity Main Features: Compressor
Up to 34 000 Nm3/h (1 020 tpd) CO • Greatest number of references in CO/N₂
separation CO
Economics • Highest safety standards for all Cold Boxes
Opex: Specific energy: • In-house technology for highly safe, highly Syngas

300 to 600 kWh/tonne reliable & highly efficient CO expander

Capex: Economics are highly dependent on • High CO recovery
the type and quality of feedstock (coal,
References
Naphtha or natural gas), as well as the
required CO purity and pressure (MDI/TDI, 32 (latest 2016)
PC, AcAc, MEG, etc.) and of the required
scope of supply Contact
hydrogen-syngas@airliquide.com

Technology Handbook Air Liquide Engineering & Construction 39

 HYDROGEN
& SYNGAS CO Cold Box – Partial Condensation
SEPARATION
Heat
Exchanger

Fuel
Application Description H₂ rich
Carbon monoxide (CO) production COCH4
Partial Condensation process is based Column
or ratio-adjusted synthesis gas production on cryogenic separation technology using the
from synthesis gas for use in chemical difference in boiling points of the main
industry Stripping
components from the synthesis gas. Column

Feedstock Feed gas is pretreated to remove impurities Syngas

Drum
Synthesis gas from natural gas/naphtha or which will freeze at cryogenic temperatures
coal/residue gasification. encountered in the process. It is then partly
condensed in heat exchangers and flashed in a
Product syngas drum before being purified step by step
CO up to 99.99% purity through distillation columns.
Every cryogenic process is tailor-made to fit the
Co-product customer’s specifications and other
Hydrogen, oxogas, methane, LNG requirements on co-products. CO
Compressor
Capacity Main Features:
• Greatest number of references in CO/N₂ CO
Up to 55 000 Nm /h (1 650 tpd) CO
3

separation
Syngas
Economics • Highest safety standards for all cold boxes
Opex: • Low specific energy consumption for wide
Specific energy: 18 to 100 kWh/tonne range of feedstock

Capex: References
Economics are highly dependent on the type
17 (latest 2017)
and quality of feedstock (coal, Naphtha
or natural gas), as well as of the required Contact
CO purity and pressure (MDI/TDI, PC, AcAc,
hydrogen-syngas@airliquide.com
MEG, etc.) and of the required scope
of supply

40 Air Liquide Engineering & Construction Technology Handbook

 HYDROGEN
& SYNGAS Liquid Nitrogen Wash
SEPARATION

MP GAN
Application Description
Synthesis gas
Production of pure synthesis gas Raw hydrogen and high pressure nitrogen are Product
for ammonia plants 3H₂=N₂
fed to the liquid nitrogen wash unit.
LNW Offgas
Feedstock Both streams are cooled down against product
gas.
Raw hydrogen
(from Amine Wash / Rectisol ™) Raw hydrogen is fed to the bottom of the
nitrogen wash column and condensed nitrogen
Product liquid is fed to the top. Trace impurities, like
Pure ammonia synthesis gas with methane, argon and carbon monoxide, are
removed and recycled as fuel gas. GN₂
a stoechiometric N₂/H₂ ratio of 1:3
Front End
To establish the desired H₂/N₂ ratio, high
Co-product pressure nitrogen is added to the process
Syngas Purification

Methane, LNG stream.

Capacity Main Features:
Up to 230 000 Nm /h (2 100 tpd)
3 • Highest safety standards for all Cold Boxes
LIN
• Low specific energy consumption
Economics for Methane / LNG co-production
Opex:
References
- LIN: 0 to 0.02 tonne/tonne of syngas
- Power: 0 to 900 kWh/tonne of LNG 49 (latest 2015)
(if LNG co-production) Contact
Capex:
hydrogen-syngas@airliquide.com
Economics are highly dependent on the
co-product requirements and required scope
of supply

Technology Handbook Air Liquide Engineering & Construction 41

 HYDROGEN
& SYNGAS Hydrogen Separation Membranes
SEPARATION

Application Description
Coalescing Filter
Recovery of hydrogen in refinery
Our membranes operate on the basis of
or chemical plants purge gas
selective permeation. Each membrane is
H₂ / CO ratio adjustment Preheater
composed of millions of polymeric hollow fibers Hydrogen
Feed Gas Hydrogen
Feedstock similar in size to the diameter of a human hair. The Rich Permeate Lean Residual
“fast gases,” or gases with a higher permeation Permeator
Any purge gas streams with hydrogen
rate, permeate through the membrane into the
concentrations >20 % (vol).
hollow interior and are channeled into the
Product permeate stream. Simultaneously, the “slower
Hydrogen (>99% vol achievable) gases” flow around the fibers and into the residue
stream. As a result, the fibers have the ability to
Co-product selectively separate a fast gas like hydrogen from
Main Features:
None carbon monoxide, methane, heavier
hydrocarbons and other slower gases • No moving parts
Capacity • Skid mounted systems cartridge
The process begins when pressurized feed gas design for simple installation
Membrane systems are truly scalable with is routed to the coalescing filter to remove
virtually no upper capacity limit Largest • Estimated payback period of less
contaminants and protect the membranes’ fiber than a year
system referenced by Air Liquide: 124 from liquid aerosols and particulates. Feed gas is
membrane cartridges • High permeability membranes for compact, low
then preheated before entering the membranes. capital system design
Economics The membranes then separate the feed into the • Unrestrained turndown capabilities
hydrogen-rich permeate and hydrogen-lean • Linear scale up for all size systems
Opex:
residue. The separation of permeate and residual • Hollow fiber membranes offer higher area to
- Dependant on feedstock quality gas is driven by the hydrogen partial pressure volume efficiency resulting in better packing
- Hydrogen recovery > 98% difference between the feed gas and permeate efficiency, smaller footprint and reduced weight
- 50% + turndown capabilities gas, as well as our advanced polymer material. and module count.
Capex: The non-porous hollow fiber membranes
1 mm to 10 + mm USD selectively allow faster molecules to permeate Contact
the membrane wall while slower, bulkier
molecules remain on the high pressure side. hydrogen-syngas@airliquide.com

42 Air Liquide Engineering & Construction Technology Handbook

 HYDROGEN
& SYNGAS Hydrogen Liquefier
SEPARATION

H2 cycle
Application Description H2 Purification Pure H2
(if required)
Liquefaction of all kinds of H₂ stream for the
Hydrogen to be treated may come from different
filling of H₂ liquid storages which ease
sources. Accordingly, source warm purification
transportation of H₂ molecules
upstream cold purification and liquefier by itself
Feedstock may be required.
Many sources : natural gas, coal, Hydrogen is precooled thanks to N₂/MR cycle
or electrolyse and the use of turbo-expander together with
cryogenic exchangers.
Product The liquefier uses BAHX (widely used in
Liquid hydrogen cryogenic gas liquefaction).
Then it is cooled and liquefied thanks to a H₂
Co-product
cycle and the use of cryogenic expanders
None together with a highly optimized cryogenic
Capacity exchangers’ arrangement. The particularity of
hydrogen liquefaction is the use of catalyst to
Up to 50 TPD
convert ortho-hydrogen into para-hydrogen in
Economics order to reduce boil-off in storage.
Opex: Boil-off from LH₂ storage is sent back into H₂ LH2 to storage Boil off from storage

Less than 10kWh/kg LH₂ cycle, in order to recover molecules.

Downstream infrastructure (storages, loading
bays, etc.) can also be supplied.

Contact
hydrogen-syngas@airliquide.com

Technology Handbook Air Liquide Engineering & Construction 43