Hydrogen

HYDROGEN
Technology Leader
As the global leader in engineering and contracting for
synthesis gas technologies, Air Liquide Global E&C
Solutions can build on vast experience in engineering,
procurement and construction of hydrogen plants.
Focusing on customized solutions that reect individual
client and project requirements, Air Liquide Global
E&C Solutions provides the full range of services from
technology packages to ownership of large scale
industrial lump sum turn key projects.
In addition to our outstanding experience of designing
over 110 steam methane reforming (SMR) units world-
wide, the integration of S/U experience, the results of
signicant R&D efforts and the long term operational
experience led from conventional SMR to the proprietary
design of todays Lurgi Reformer

technology.
Safety and Environment
Air Liquide Global E&C Solutions hydrogen plants are
designed to meet the most stringent international safety
and environmental standards throughout the design,
construction and operation of the plant.
Customized Solutions
The majority of hydrogen produced worldwide is
consumed in reneries and petrochemical industries.
Hydrogen is also used as transportation fuel and for a
large number of industrial processes such as the
production of metals, electronics, edible fats and oils,
or production of oat glass.

This variety of established and future oriented hydrogen
offtakers leads to solid growth rates in global hydrogen
demand, of which today more than 95 % is covered by
units applying SMR of hydrocarbon feedstocks.
Renery and chemical companies have various options
to cover hydrogen demands including:
Recovering hydrogen from renery fuel gas or chemical
unit off-gases
Revamping existing steam reforming units
Building and operating a new steam reforming units
Opting for an alternative hydrogen production
method such as gasication technology
Importing hydrogen over the fence from an industrial
gas supplier
With cutting-edge
technologies and services
to dene your solution.
2 Hydrogen
For all options, Air Liquide Global E&C Solutions
commands the full range of engineering services to
develop the optimum technology solution for the
individual client concept.
The project specic customization process for Lurgi
Reformer

typically includes:
Closest cooperation with client representatives
Optimization of export steam fows with regards to
cost and efciency
Optimization of the integration of new units into
existing site concepts
Optimization of the generic plant concept, e.g. with
regard to co-generation of complementary products
such as CO, NH
3
or MeOH
Optimization of project implementation schedule
Optimization of plant pre-fabrication and modular-
ization concepts
Optimization of plant design with regard to multiple
feedstock utilization
Optimization of plant availability and reliability with
regard to capital expenditure
In a nutshell the Lurgi Reformer

technology provides:
Proven technology
Highly customized design solutions
Easy and smooth operation
Superior fring and load control
Best in class emission levels
The Lurgi Reformer

is especially outstanding due to:

Top fred reformer box
High energy effciency
Operational availability higher than 99 %
High operational reliability ensured by 2 out of
3 voting systems
Optimized turn-around cycles
Low utility consumption
Low maintenance costs
Low overall capital expenditure
Hydrogen 3
The generic process scheme comprises feed desulfur-
ization, SMR, shift conversion and hydrogen purication.
The hydrocarbon feedstock is mixed with recycled
hydrogen. Desulfurization comprises two process
steps, organic sulfur compounds are converted to H
2
S
in the presence of a hydrogenation catalyst and
H
2
S is adsorbed.
The desulfurized feed is mixed with process steam at
an optimized steam to carbon ratio and superheated
prior to entering the primary reformer. In the presence
of a catalyst the mixed feed is converted to a reformed
synthesis gas containing H
2
, CO
2
, CH
4
, N
2
and steam
inside the tubes of the primary reformer.
The CO in the reformed synthesis gas is water gas shifted
for increased hydrogen yields by means of sweet water
gas shift process units such as high temperature shift
or high temperature shift plus low temperature shift
process units.
In the hydrogen purication unit, hydrogen is separated
from the shift gas stream by pressure swing absorption
or membrane units to provide continuous and constant
hydrogen product ow rates.
The reformer box is heated by ring the off-gas from the
hydrogen purication unit and by make-up process fuel
with forced draught burners in the top section.

The combustion air required is routed by a combustion
air fan to the burners after pre-heating. The hot ue
gases exit the reformer box through a refractory-lined
duct and are routed to the ue gas stack after excess
heat being recovered in the heat recovery section.
Steam generated by waste heat of reformed gas from
the SMR is utilized as process steam while the excess
is exported.
Process Scheme
Heat Recovery
Feed Fuel
HYDROGEN
Desulfurization
Pre-reforming
(optional)
Steam Reforming
Shift Conversion
Pressure Swing
Adsorption (PSA)
Export Steam
Process Steam
Demineralized
Water
Flue Gas
4 Hydrogen
To achieve an optimum customization of the Lurgi
Reformer

plant design, Air Liquide Global E&C Solutions

offers a full range of process options.
Pre-Reforming
For the conversion of higher-molecular hydrocarbons
and optimization of overall energy efciency, Air Liquide
Global E&C Solutions offers tailor-made pre-reforming
process units as an integral part of the hydrogen plant.
Autothermal Reforming
Pure autothermal reforming can be applied for syngas
generation whenever light natural gas and oxygen are
available as feedstocks. The desulfurized and optionally
pre-reformed feedstock is reformed with steam to syn-
thesis gas at high pressures using oxygen as reforming
agent. The process yields carbon-free synthesis gas
and offers great exibility over a wide operating range.
The synthesis gas is compressed by a single casing
compressor with integrated recycle stage to the required
battery limit pressure.
As the industry leader in autothermal reforming, we
present a large number of plant references starting as
early as the 1950s.
Combined Reforming
For heavy natural gases and oil-associated gases, the
most economic way to produce synthesis gases is a
combination of autothermal reforming and steam
reforming. After desulfurization, a branch of the feed
gas is processed in a steam reformer at high pressure
and relatively low temperature. The reformed gas is then
mixed with the bypassed feed gas and reformed to
synthesis gas at high pressure in the autothermal reformer.
This concept has become known as the Lurgi Combined
Reforming process.
The main advantages of the this Combined Reforming
process is the feed gas bypass of the steam reformer
and the low process steam consumption translating into
reduced energy consumption as well as lower capital
expenditure.
Process Options
Looking back on decades
of operational expertise, we
develop competitive solutions
for our customers.
Hydrogen 5
Success through Technology
Partial Oxidation
Air Liquide Global E&C Solutions proprietary Multi
Purpose Gasifcation MPG

technology is suited for the

non-catalytic partial oxidation of solids, gaseous or
liquid feedstocks for the production of large quantities of
synthesis gas. With over 45 years of active experience
in gasication technologies and over 75 units on-stream,
Air Liquide Global E&C Solutions is the right partner to
maximize advantages of the MPG

technology due to:

Maximum feedstock fexibility
Extended guaranteed burner lifetimes
Inherent plant safety by pressurized cooling water
system
Long reactor lifetimes due to moderate, uniform
wall temperature proles
Sophisticated designs for boiler and quench
conguration
In combination with raw gas shift and raw gas purication
technologies, MPG

is the superior choice for large

scale hydrogen plants based on heavy residue feed-
stocks such as oil sands, vacuum residues, visbreaker
residues or asphalt.
Water Gas Shift
Depending on the process optimization with regard to
steam requirement, feedstock type and quality, and fuel
valuation, Air Liquide Global E&C Solutions proposes
the optimum solution for water gas shift systems:
For hydrogen plants designed for boiler mode operation
by sweet water gas shift process units with upstream
feedstock desulfurization:
High temperature shift followed by a hydrogen
purication
High temperature shift followed by a low temperature
shift and methanation process steps
Medium temperature shift followed by a hydrogen
purication
For hydrogen plants designed for quench mode
operation by a raw gas shift process unit followed by
a synthesis gas.
Hydrogen Purication
Depending on process conditions, required hydrogen
quality and plant capacity, Air Liquide Global E&C
Solutions offers three options for the hydrogen purication
process step:
Pressure swing adsorption (PSA) as the standard
solution
Low temperature shift plus downstream methanation
process units for hydrogen plants with high hydrogen
yields
Membrane units for low capacity hydrogen units or
hydrogen units with specic quality requirements
6 Hydrogen
Lurgi Reformer

The heart of the hydrogen plant is the Lurgi
Reformer

. Air Liquide Global E&C Solutions

advanced design combines outstanding
operational characteristics with excellent
maintenance features leading to superior
operability and low investment and operating
costs.
Distinct features of the Lurgi Reformer

proprietary design are:
Large single train capacities of up to
1,000 tubes per train available
Top fred reformer box for minimum
number of burners
Horizontal convection section for
reduced maintenance efforts
Cold header design for minimized
thermal stress and refractory protection
Flexitube design for higher design and
operating temperatures
Counter-weight tube support design for
minimized mechanical stress
Horizontal or vertical waste heat recovery
system designs available
High modularization levels for increased
quality of mechanical equipment,
piping and instrumentation
Lurgi Reformer

Steam Generation
Reformed Gas Collector
Combustion Air
Reformer Feed
CO
2
Capture
Our proven and worldwide recognized technology
portfolio of CO
2
capture technologies include physical
or chemical washes such as:
Rectisol

MDEA
Amine washes
Emission Control
Reecting increased requirements of environmental
regulations and clients or project policies, Air Liquide
Global E&C Solutions offers a toolbox of technologies
to lower the environmental impact of hydrogen plant
operations which includes:
State of the art noise abatement
In-house portfolio of worldwide recognized CO
2

capture technologies
Inherent plant safety by pressurized cooling water
system
Expertise in NOx reducing burner technologies
Latest generation of selective catalytic reduction
technologies (SCR) to minimize nitrous oxide ue
gas emissions
Hydrogen 7
Air Liquide Global E&C Solutions is setting best in class
standards with regards to plant availability and reliability by:
Integrating design experience from over 110 Lurgi
Reformer

units and over 1 million hours of operation

in more than 30 Air Liquide hydrogen plants.
Conducting extensive availability studies during the
design phase of each project
Typical designs resulting in on-stream factors larger
than 99 % for normal operation
Proven designs for turn-around cycles of up to
5 years
Hydrogen Quality
The hydrogen produced is of high purity 99.999.999 vol. %,
with low impurity levels, such as a CO content below
10 vol. ppm.
Utility Consumption
For a Lurgi Reformer

based medium sized hydrogen

plant utilizing light natural gas as feedstock, typical
consumption gures per 1,000 Nm
3
hydrogen product
amount to:
Feed and Fuel 400 420 Nm
3

Make-up BFW 1.01.5 t
Cooling Water 2.53.0 Nm
3

Electricity approx. 17 kWh
Export Steam 0.600.90 t
Typical consumption gures vary depending on hydrogen
quality, customization and optimization of the plant
design and export steam valuation.
Load Control
Fully automatic blend and change of various feed-
stocks
Fully automatic load changes up to 3 % capacity
per minute
Operation at minimum steam to carbon ratios
Firing Control
Peaks of PSA tail gas fow and composition are
compensated by fuel gas
Stable reformed gas temperature ensured
Minimum oxygen content in the fue gas ensured
Availability and Reliability
8 Hydrogen
Cost Efciency
Lurgi Reformer

technology is the result of optimization

and customization processes with regard to capital and
operational cost.
The Lurgi Refomer

offers reduced capital expenditure

due to:
Top fred designs
Multiple tube rows limiting the number of burners
Large single train plant capacity
High level pre-fabrication and modularization
Lurgi Refomer

design results in reduced operating

cost due to:
High operating pressures at the Lurgi Reformer

outlet
High feed preheating temperatures
Completely maintenance free catalyst tube
inspection system
Advanced Hydrogen Management
Advanced hydrogen management systems are the key
to hydrogen plant efciency and availability. The Lurgi
Reformer

features the most sophisticated control

systems resulting in exceptionally high on-stream factors.
PRO-EN Services
Proftability enhancement services are the backbone
of hydrogen optimization and management solutions.
Customized, proprietary state of the art simulation
software offers industry-leading hydrogen optimization
studies that are customized to meet client and project
needs and budgets.
Design Tools
Air Liquide Global E&C Solutions applies state-of-the-art
plant engineering and software tools such as
3D modeling. Computational Fluid Dynamics (CFD)
models are used to generate optimized design solutions
at different scales: from the distribution piping to
the full furnace using a dedicated in-house 3D tool.
In addition, our multi-scale computational approach
helps creating new mathematical models for complex
uid designs.
We design
a true partnership.
CFD Model Sipchen
Hydrogen 9
References
The benet of long years of engineering experience for
steam reforming plants is available and applied in order
to achieve optimum results.
Plant capacities up to 250,000 Nm
3
/ h hydrogen
production
Worldwide more than 30 hydrogen reference plants
Worldwide more than 110 Lurgi Reformer

reference
plants
Over 120 years of engineering experience

Intelligent Solutions
Around 4,000 employees are working for Air Liquide
Global E&C Solutions world-wide. More than 15 % are
engaged in nding technological solutions in the com-
panys technology and R&D units. After all, each client
and each project have their own specic design and
operational conditions calling for intelligent and integrated
concepts. The aspects of feedstock availability and quality
are discussed in multidisciplinary teams of experts to
optimize solutions with best-in-class engineering practices.
Process optimizations require concrete numerical data,
computer assisted simulation results and considerable
experience. This expertise is indispensible when deci-
sions have to be made. Air Liquide Global E&C Solutions
contributes to every project the know-how accumulated
in more than 50 years of engineering experience for
synthesis gas plants.
We design the
worlds most advances
innovative solutions.
Operational Excellence
Engineering Center of
Air Liquide Global E&C Solutions
10 Hydrogen
Competence in Project Execution
Air Liquide Global E&C Solutions execution centers
around the world allow for a fast and efcient support of
clients and projects in their respective location. Modern
communication structures, fast know-how transfer and
the complete service portfolio are the key to success for
our clients and projects.
Scope of Services
Air Liquide Global E&C Solutions provides technology
solutions executed in full-service operating centers
worldwide. Our activities cover all phases of synthesis
gas projects from nancing through design, procurement,
start-up services and operation including:
Consulting services
Market studies
Conceptual studies
Feasibility studies
Product marketing
Financing
Investment analysis
Contracting
Value engineering
Authority engineering
Basic and detail engineering
Global sourcing
Construction
Construction supervision
Start-up services
Operation and maintenance
Technical services
In addition, project management consulting services
are offered to provide comprehensive project manage-
ment and associated services for large scale synthesis
gas projects.
About Air Liquide Global E&C Solutions
Hydrogen 11
E&C Communications, 57 avenue Carnot, BP 313, Champigny-sur-Marne 94503, FRANCE
Air Liquide is the world leader in gases for industry, health and the environment, and is present in 80 countries with 46,200 employees. Oxygen, nitrogen, hydrogen
and rare gases have been at the core of Air Liquides activities since its creation in 1902. Using these molecules, Air Liquide continuously reinvents its business, anticipating the
needs of current and future markets. The Group innovates to enable progress, to achieve dynamic growth and a consistent performance.
Innovative technologies that curb polluting emissions, lower industrys energy use, recover and reuse natural resources or develop the energies of tomorrow, such as hy-
drogen, biofuels or photovoltaic energy Oxygen for hospitals, homecare, ghting nosocomial infections Air Liquide combines many products and technologies to develop
valuable applications and services not only for its customers but also for society.
A partner for the long term, Air Liquide relies on employee commitment, customer trust and shareholder support to pursue its vision of sustainable, competitive growth. The
diversity of Air Liquides teams, businesses, markets and geographic presence provides a solid and sustainable base for its development and strengthens its ability to push
back its own limits, conquer new territories and build its future.
Air Liquide explores the best that air can offer to preserve life, staying true to its Corporate Social Responsibility and sustainable development approach.
In 2011, the Groups revenues amounted to 14.5 billion, of which more than 80% were generated outside France. Air Liquide is listed on the Paris Euronext stock exchange
(compartment A) and is a member of the CAC 40 and Dow Jones Euro Stoxx 50 indexes.
Copyright Air Liquide Global Engineering & Construction Solutions, 309e Hydrogen / 12.05. / 4
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