REFINING
Hydrogen technology–
an overview
Developments in the area of hydrogen production equipment, configurations,
catalysts, materials and automation have brought about improved operational
reliability and effluents curtailment, as well as achieving lower operating costs
H
ydrogen plays a foremost role in
the various hydroprocessing
operations within oil refining
and is considered as a critical compo-
nent in determining the type and qual-
ity of the refinery products slate. In fact,
the configuration and complexity of a
refinery is often defined by the extent
of its usage. The past decade has seen a
remarkable growth in hydrogen
demand for meeting the ongoing envi-
ronmental regulations for cleaner and
lighter transportation fuels.
In the coming years, several develop-
ments are taking shape for paving the
way to the so-called hydrogen economy
in relation to hydrogen-based energy
systems, with keen deliberations going
on for sustainable hydrogen in the
longer term.
The other major use of hydrogen has
been as synthesis gas or syngas (its mix-
ture with other gases like nitrogen or
carbon-monoxide) for the manufacture
of bulk chemicals like ammonia and
methanol and for speciality chemicals
like oxo-alcohols, MDI/TDI etc. Further,
hydrogen finds substantial use in the
metal industry as a reducing medium in
the production of direct reduced iron
and steel making.
Current global production of hydro-
gen, either in its pure form or as syngas,
3
is in the range of 60 million Nm /h,
which is equivalent to about 55 billion
scfd or 130 000tpd. Roughly one-third
of it is generated as on-purpose hydro-
gen for refineries and another third is
produced (as contained hydrogen) in
the form of syngas for the chemicals
industry. The remaining is divided (in
decreasing order) over in-situ hydrogen
produced within the refineries (from
catalytic reforming) and olefins com-
plexes, reducing gas for metals/steel
industry and the various consumer
industries like edible fats, textile and
pharmaceuticals.
The emerging needs on hydrogen
generation and its management have
driven concerted advances in some of
the key areas of hydrogen technology,
Sanjiv Ratan
Technip-Coflexip
also setting the ground for some inno-
vative developments. Apart from the
typical stimulus for better cost effective-
ness and operating efficiency, the major
focus has been towards enhancing plant
reliability, safety and operational flexi-
bility, compactness of equipment, ease
of operation and, undoubtedly, the gov-
erning environmental factors.
Production technologies
Over the years, hydrogen has been
mostly produced from hydrocarbon
feedstocks ranging from natural gas to
coal. A very small portion has been pro-
duced from water by electrolysis. For
hydrogen generation, plant capacities
3
could range from as low as 100Nm /hr
3
to over 220 000Nm /hr (0.1 to 200 mil-
lion scfd). In the smaller capacity range,
hydrogen production by electrolysis of
water or dissociation of ammonia and
methanol can be justified and econom-
ical based on modular units.
However, as hydrogen capacities
3
increase (above 500Nm /hr), the hydro-
carbon route generally begins to be
more attractive based on overall eco-
nomics. Moreover, for higher capacities
3
(above 5000Nm /h), the modular
approach becomes attractive.
The process for manufacturing
hydrogen from hydrocarbons (on-pur-
pose hydrogen production) usually con-
sists of four major sections, including
feed preparation and pre-treatment,
syngas or raw hydrogen generation,
water-gas shift conversion and final
purification.
The core section from the point of
view of criticality, capital intensity and
efficiency relates to the syngas genera-
tion. Hence it encompasses different
processing routes and technology
options whose selection mainly
depends upon available feedstocks and
utilities, capacity, site-specific condi-
tions/requirements and, of course,
overall economics.
The major and commercially proven
processes available for producing (syn-
gas for) hydrogen are steam reforming
53
P T Q AUTUMN 2003
w w w. e p t q . c o m
(SMR), partial oxidation and auto-ther-
mal reforming.
These processes differ mainly in the
range of applicable feedstocks as well as
the basic reactants in terms of steam
and/or oxygen for producing the raw
hydrogen-rich syngas.
Steam reforming (SMR) of hydrocar-
bons (ranging from light natural gas up
to heavy naphtha) has been the pre-
dominant route for the production of
raw hydrogen. It has been the most
widely employed process and has
remained the technology of choice over
the past five decades, accounting for
more than 90% of the global hydrogen
generation capacity, which is
attributable to being well-proven, reli-
able, simple to operate, and which
offers significant flexibility in feedstock,
apart from being cost-effective.
The basic reactions taking place can
be represented by:
CnHm + nH2O → nCO + (n+m/2) H2
(Endothermic steam reforming; n <7)
nCO + nH2O = nH2 + nCO2 (Exothermic
water-gas shift conversion)
For paraffinic feeds, m = 2n + 2 and only
in the case of methane, the reaction
becomes an equilibrium reaction. The
net overall reaction is still highly
endothermic and based on its thermo-
dynamics, it is favoured by higher steam
to carbon ratio, higher temperature and
lower pressure.
Based on the intrinsic need for sub-
stantial heat input and high tempera-
tures, as well as kinetics-limited
catalytic space velocities, steam reform-
ing is typically conducted in a tubular
reactor with high level heat input by
fuel firing. It typically employs a fire-
box type reformer containing catalyst-
filled tubes through which preheated
feed-plus-steam flows to produce an
equilibrium mixture of hydrogen, car-
bon-oxides along with the residual
methane and steam.
The SMR process, as well as reformer
tube integrity, is strongly dependant on
catalytic activity and stability. Hence,

proper selection and application of cat-
alysts play an important role in the per-
formance and reliability of the process.
Partial oxidation (POx) technology is
based on incomplete oxidation of
hydrocarbon, usually using oxygen
with little or no steam:
CnHm + n/2 O2 → m/2 H2 + nCO
The sub-stoichiometric combustion
limits the degree of oxidation of CO
and H2 to CO2 and H2O, respectively,
thus providing syngas with lower
H2/CO ratios. It is a non-catalytic oper-
ation, which allows much higher tem-
peratures and is therefore applicable
particularly for processing heavy-end
feedstocks.
Oxygen and hydrocarbon are mixed
in a burner and allowed to react at con-
ditions. The process can use a variety of
feeds ranging from natural gas to heavy
residues within the refinery. To enhance
on-stream reliability, usually more than
one train of gasifiers are employed to
improve plant availability.
For heavier feeds, which also tend to
contain higher levels of sulphur and
other trace impurities like (heavy) met-
als etc, elaborate steps are needed for
carbon/slag handling and downstream
processing in terms of H2S and CO2
removal, as well as process condensate
treatment. Further, since the POx pro-
cess is based on high-pressure internal
combustion, it does not call for a large
external heat input (except for pre-heat-
ing of the reactant streams). According-
ly, conventional purification schemes
based on machination routes become
more suitable compared to PSA, to
avoid the purge gas fuel (albeit at low
levels), as well the loss of hydrogen in
purge gas.
The economics of hydrogen genera-
tion via POx is governed by the price
and/or availability of oxygen and the
credit for using lower grade (heavier)
feedstock. For processing of lighter feed-
stocks ranging from natural gas to refin-
ery offgas, the POx route can be
relatively simpler, more cost effective
and reliable, especially for hydrogen-
carbon monoxide (Hy-CO) production.
Heat recovery features either direct
quench or indirect steam generation.
The auto-thermal reforming (ATR)
process is a sort of combination of POx
and SMR in one reactor. The feed hydro-
carbon mixed with some steam is par-
tially combusted with oxygen, followed
by steam reforming over the catalyst
bed within the same vessel. The heat of
combustion is utilised to conduct the
endothermic reforming reaction to
almost complete conversion without
any external heat input (auto-thermal-
ly), hence the name.
The ATR applications are also largely
REFINING
Recycle H2
compressor
Recycle H2
Make-up fuel
HC
feed
Pre- Pre-
treatment reforming
(optional)
Export steam
Steam
system
30 400 550
Figure 1 Generic hydrogen plant flowsheet based on SMR-PSA
dependent on the oxygen price and
case-specific economics, especially for
HyCO production.
SMR becomes the straightforward
choice in the case of non-availability of
oxygen and feedstock (up to naphtha).
In other cases, especially in relation to
Hy-CO credits, it could require a
detailed study to evaluate the overall
economics. Generally, factors like econ-
omy of scale, low-grade heavy feed,
cheap oxygen, credit for CO and added
value for captive/export power could
favour POx/ATR in specific cases. Never-
theless, it is generally acknowledged in
the industry that steam reforming is the
technology of choice for hydrogen pro-
duction.
The downstream processing of the
reformed gas primarily proceeds
through the steps of shift conversion
and hydrogen purification using pres-
sure swing adsorption (PSA) and related
waste-heat recovery plus cooling. PSA
technology completely replaces the
conventional CO2 removal plus metha-
nation route and has been the industry
norm for over two decades. It provides
high purity hydrogen (99.99% or even
higher) in a single system operating at
ambient temperatures and without any
heat input.
The steam reforming together with
PSA purification carries inherent inte-
gration of the back-end and the front-
end through the use of PSA purge gas as
primary fuel in the reformer. Such link
not only results in the reutilising the
unconverted feed as fuel but offers sig-
nificant scope for optimising the level
of feed conversion without affecting
hydrogen purity and thus helps in
achieving the desired objectives of pro-
cess optimisation, flexibility and relia-
bility. Thus, depending upon the
relative pricing of feed and fuel or
imposed utilisation of any specific
54
P T Q AUTUMN 2003
Purge gas fuel
Hydrogen
Shift product
Reforming PSA
conversion
900 400 40 Temperature, °C
quantity of low-grade make-up fuel, the
feed conversion can be adapted
Catalyst developments
The hydrogen process based on steam
reforming is strongly driven by the cat-
alytic steps. Hence, proper selection and
performance of catalysts play an intrin-
sically important role in optimisation
and reliability of the process. Also the
feedstock flexibility of steam reforming
has been widely increased with the
application of the pre-reforming step
upstream from the reformer.
Notable improvements have been
made in the catalysts applied in hydro-
gen-syngas plants, mainly to respond to
the sought-after needs and desired char-
acteristics that include:
— Higher resistance to poisons and pro-
cess upsets
— Catalyst shapes for higher activity
and lower pressure drop
— Higher space velocities
— Longer operating life
— Broader range of operating condi-
tions
— Easier startup (and reduction require-
ments)
— Better selectivity (reduced formation
of undesired by-products).
And specifically for the reforming
catalysts:
— Better resistance to carbon formation
while maintaining activity
— Improved thermal stability and
mechanical strength
— Better fixation of potash in alkalised
catalysts (minimised migration)
— Increased resistance to excursions on
steam and temperature.
The typical process configuration of a
state-of-the-art hydrogen plant consists
of the following process steps (Figure 1):
— Feed pre-treatment
— Pre-reforming (optional)
— Reforming

— CO Shift conversion
— Purification by PSA
Feed re-treatment
Reforming (also pre-reforming) catalyst,
is most susceptible to poisoning by sul-
phur and chlorine compounds. Hence
these components need to be removed
from the hydrocarbon feed to very low
levels (down to <100ppb level) prior to
reforming step.
When using heavier feedstocks (such
as SR naphtha) extra provisions are
needed for removal of possible contami-
nants like non-reactive organic sulphur
and chlorine compounds, unsaturates
and heavy metals etc. Feed pre-treat-
ment normally consists of a hydrogena-
tion step (Comox or Nimox) to convert
organic sulphur to H2S (and organic
chlorides if present, to HCl) followed by
H2S absorption using Zinc oxide (ZnO).
For sulphur removal loads (above
5–10t/year) two ZnO reactors in
lead/lag arrangement are preferred,
which apart from maximising sulphur
pickup, offer online catalyst
changeover, thus allowing extended
continuous cycle on-stream runs. In
case of quite high concentrations of sul-
phur, generally in naphtha feedstocks
(up to 1000ppm and over) a pre-desul-
phurisation unit is employed in terms
of (primary) hydrogenation followed by
thermal stripping for bulk removal of
H2S, in order to minimise the recurring
cost of ZnO as well as spent catalyst
disposal.
In a refinery environment, several
hydrocarbon streams that do not quali-
fy for cost-effective hydrogen recovery,
generally end up in the refinery fuel
net. However, after proper techno-eco-
nomic assessment based on their com-
position (including contaminants),
their available pressure and their quan-
tity, some of these streams can be effec-
tively utilised as feedstock for hydrogen
production.
It can often involve compression,
olefin saturation in combination with
hydrogenation of organic sulphur and
chlorine compounds, if any. In the case
of high levels of unsaturates, a dedicat-
ed recycle loop is usually applied
around the hydrodesulphuriser (HDS)
reactor for diluting the inlet stream and
eventually to remove the exothermic
heat of reaction. However, the econom-
ic attractiveness depends upon the
added value to the “fuel towards feed”
(or savings in the hourly operating cost)
versus the costs of off-gas conditioning.
In the case of multiple feedstocks, it
becomes critical to define the design
basis and operational modes for the
feed pre-treatment. It mainly involves
establishing the controlling and/or
worst-case design rating, required oper-
REFINING
reformer
Process steam
Desulphurisation
HC feed
Figure 2 Pre-reformer integration
ating parameters’ window (mainly level
of recycle hydrogen and temperature)
and their effective control philosophy
under various operating cases. More-
over, special attention needs to be given
for proper transition and control during
capacity and/or feedstock change.
Pre-reforming
Feedstock flexibility in SMR has been
widely enhanced by advances in direct
reforming catalysts as well as applica-
tion of pre-reforming upstream from
the reformer. Over recent years, pre-
reforming has acquired increasing
application in a refinery environment
for achieving multiple feedstock flexi-
bility, from natural gas to captive liquid
hydrocarbon streams such as LPG and
naphtha, in an efficient and reliable
manner.
Pre-reforming is a low-temperature
(approximately 400–550ºC) adiabatic
reforming step applied upstream from
the reformer for achieving a variety of
objectives. To achieve low-temperature
activity, a highly active catalyst is
required, converting a wide range of the
previously mentioned hydrocarbon
feedstocks into a methane-rich gas in
the presence of steam.
The pre-reforming operation is the
net result of two competing equilibrium
reactions, namely steam reforming
(endothermic), and methanation of
hydrogen with carbon oxides (exother-
mic). Hence, the temperature profiles
along the catalyst bed are different for
different feedstocks depending upon
the inlet conditions and methane equi-
librium. To achieve the required tem-
perature window for different operating
cases, part of the process steam is added
57
P T Q AUTUMN 2003
Pre-
Primary
reformer
as post steam injection, which also
helps during transient conditions
Incorporation of a pre-reformer
allows higher reformer inlet tempera-
tures (up to 650 ºC) without the con-
cern for thermal cracking due to the
absence of the C2+ fraction. Hence, it
inherently offers the potential for fur-
ther reheating reformer feed, thus shift-
ing the reformer radiant heat duty to
convective mode. This shift can reduce
the size of the reformer by 5–15%,
depending upon the feedstock and the
operating conditions for the reheat
potential. Another related advantage is
the reduction in steam export against
fuel savings, which can prove quite
attractive in some cases.
Overall, pre-reforming of naphtha
feed can improve the net thermal effi-
ciency of hydrogen production by
1–4%, depending upon the type of feed
and selected operating conditions.
However, the hourly operating costs are
more sensitive to the relative price of
export steam against fuel. On the other
hand, pre-reforming is an additional
process step and with significant cata-
lyst life-cycle costs. Hence its applica-
tion needs to be evaluated on a
case-to-case basis to ensure overall eco-
nomics while satisfying specific plant
requirements.
A simplified scheme of pre-reformer
integration is shown in Figure 2.
Plants using natural gas as one of the
feedstocks have the possibility of on-
line catalyst renewal by isolating and
bypassing the pre-reformer, while oper-
ating on natural gas at reduced capa-
city (~70%). For cases where extended
continuous operation is required on
heavy (liquid) feed, the twin-reactor

configuration in parallel is applied,
with one reactor as stand-by. This not
only takes away the limitations on the
continuous operation run through
online switching of the exhausted reac-
tor, but also offers lower annual catalyst
costs and some operational advantages
during start-up and shutdown.
Reforming
Steam reforming of hydrocarbon feeds
is generally limited up to heavy naph-
tha (C7) in view of the catalytic require-
ments and the potential carbon
formation. Direct reforming of multiple
and/or heavier feedstocks with widely
differing carbon number (CN) requires
major attention in simulating the car-
bon margin, which signifies the depar-
ture from the carbon equilibrium in the
reformer tubes based on thermodynam-
ic and kinetic conditions.
There is a range of available reform-
ing catalysts that can achieve the
desired carbon margin through specific
combinations of alkalised and non-alka-
lised catalyst in order to achieve the
proper alkali profile and the related cat-
alyst activity.
Important considerations such as
steam-to-carbon (S:C) ratio, inlet tem-
perature and the applied heat flux need
to be addressed for proper design in
order to achieve effective and reliable
performance. The reforming process is
carried out in tubular reactors that are
highly endothermic and catalytically
controlled. Heat is supplied by the
burners in the furnace box and trans-
ferred to the catalyst tubes mainly by
radiation.
Water-gas shift
CO shift conversion, also commonly
known as water-gas shift (WGS) is
applied for increasing hydrogen yield
through conversion of residual carbon-
monoxide to hydrogen and carbon-
dioxide in the presence of steam over
iron and/or copper-based catalyst. Ther-
modynamically, lower operating tem-
peratures are favourable for shift
conversion, and thus has the following
impact:
— Reduction in feed rate (better feed
conversion)
— Increase in makeup fuel (reduced
heating value of PSA purge gas)
— Additional export steam (exothermic
heat).
Over the years, advances and devel-
opment efforts in shift catalysts have
been in terms of specific performance,
extended activity and operational
aspects, such as resistance to upsets and
reduced by-products formation.
The CO in the hydrogen product is
considered as an undesirable impurity
or even as a poison in most of its refin-
REFINING
ery end-uses. Generally, older hydrogen
plants based on conventional purifica-
tion route involved the two-stage CO
shift conversion based on high temper-
ature (HT) followed by low temperature
(LT), in order to get down to low levels
of CO-slip, which could be handled in
the downstream methanation step.
However, later hydrogen plants based
on PSA purification, mostly employed
only HT shift, since the product hydro-
gen purity is largely independent of the
CO level in the process gas, and all the
CO is removed in the PSA purge gas.
The HT shift reactor typically oper-
ates on an inlet temperature of
320–350°C for bulk conversion of car-
bon monoxide to hydrogen, with typi-
cal exotherm of 50–80 C and the
corresponding CO-slip between 3–6
vol% (dry) in relation to the inlet
steam/gas ratio being between 0.4–0.6.
The newer catalyst formulations have
been promoted with some copper,
which apart from improving the activi-
ty, also helps against the potential Fish-
er-Tropsch (F-T) side reactions as well as
the extent of catalyst sintering in rela-
tion to steam/gas ratio.
Addition of the LT shift in a hydro-
gen plant becomes more of an optimi-
sation decision, mainly in cases where
the feed is more expensive than fuel. As
a relatively recent development, medi-
um temperature (MT) shift catalyst has
been applied in some of the hydrogen
plants but there has been limited expe-
rience in view of some of the demerits
in terms of temperature sensitivity v/s
activity and by-product methanol for-
mation etc.
The LT shift reactor operates typically
with inlet temperatures of around
200°C and employing copper-based cat-
alyst, which is more sensitive to sulphur
poisoning and thermal stability. In view
of allowable temperature of less than
250ºC, LT shift needs to be applied
downstream of a HT shift converter to
limit exothermic temperature rise
across the catalyst bed.
For larger hydrogen plants, it is some-
times justifiable to install a LT shift con-
verter to improve overall efficiency
and/or operating costs, especially in
cases where the fuel is cheaper than
feed. The justification for LT shift is
plant-specific and needs proper evalua-
tion in each case based on relative pric-
ing of feed, fuel and steam.
Application of medium temperature
(MT) shift step allows combining the
HT and LT shift in one step. Another
advantage rests in being copper-based,
which allows lower S/C ratios in the
upstream reformer without the con-
cerns of catalyst sintering and unde-
sired F-T side-reactions, typical of
Fe-based HT shift catalyst. On the other
58
P T Q AUTUMN 2003
hand, it suffers from inherent concerns
of susceptibility to higher temperature
(above 350ºC) based on the larger
exotherm due to one step conversion,
especially on larger CO loads on heavier
feedstocks for retaining stable activity.
Secondly, it tends to have higher
methanol formation due to favourable
kinetics, which ends up in the process
condensate. Being sensitive to tempera-
ture excursions, it requires extra atten-
tion to design, control and operation,
especially during transient conditions
of start-up and/or feedstock change.
The CO slip from MT shift is lower
than HT shift, but still reasonably high
compared to LTS due to much higher
exit temperature as well end-of-run
approach to equilibrium. Thus, it results
only in a marginal net (feed + fuel)
reduction of say between 0.3 to <1.0% .
PSA purification
The PSA process is based on the princi-
ple of relative diffusion and the fact
that specific molecular adsorbents are
capable of binding or letting through
different gaseous molecules with differ-
ent affinity, depending upon their par-
tial pressure, size and polarity.
Accordingly, the various impurity com-
ponents can be adsorbed at a higher
pressure and desorbed by “swinging” to
a lower pressure.
As such, a PSA operation is a batch
process with the adsorber going
through various stages of depressurisa-
tion in a fixed cycle time. However, by
using multiple adsorbers on a
sequenced basis, constant on-spec prod-
uct flow is maintained. Commercial
units have normally between four and
12 vessels, depending upon the capacity
and desired hydrogen recovery.
Hydrogen is almost non-adsorbed,
which gives PSA system the unique
capability of producing very high purity
hydrogen product of 99.99%+ and on a
pressure close to the feed pressure. The
effect of increased H2 purity on hydro-
gen recovery is minimal. However, the
hydrogen recovery is quite sensitive to
the tail gas pressure, which is usually
drawn between 20 to 40KPag, providing
recoveries between 84–90%, depending
upon the number of vessels and pres-
sure equalisations.
PSA system offers unmatched opera-
tional flexibility against upstream fluc-
tuations in terms of feed composition
and/or flow swings. It retains product
hydrogen purity as well as recovery up
to 30% turndown.
The PSA systems are very reliable and
versatile, needing very little mainte-
nance due to absence of moving parts
(except on/off valve stems). On-stream
factors in excess of 99% have been often
demonstrated. Also, the operating life
 REFINING

of the adsorbents used is in reduced by preheating the

excess of 10 years and can last combustion air and further by
for the typical plant life. In employing a pre-reformer,
addition, in case of any mal- which add to additional
function like pressure error or Feed inlet equipment and related capital
a valve failure, the units are pigtails cost. Also, some of the process
generally provided with the parameters like S:C ratio,
capability to operate with excess air level, extent of heat
reduced number of beds, Burners recovery etc, can also be
bypassing the failing section adjusted to regulate the
Multiple
automatically, while main- tube lanes export steam amount.
taining hydrogen purity with Even if the export steam is
only slight loss of recovery. valued as equivalent of fuel
PSA systems operate on Flue gas to cost, a plant that produces
fully automatic using micro- convection less export steam tends to
processor-based PLC units. Outlet pigtails section become less efficient, since
The level of automation can Transfer line the low-level heat recovery
Process gas
be extended to online purity to PG boiler
and integration cannot be
control, which offers fully utilised. However, the
improved H2 recovery and export steam philosophy is
stabilises sudden fluctua- mostly governed/imposed by
tions, thus also enhancing Figure 3 Schematic of typical large top-fired reformer the site-wide steam-power
the reliability of PSA units. balance and the specific eco-
Considerable advancements have been and use of non-metallic ferrules in the nomics in terms of evaluation against
made in the design, operation and inte- process gas boiler. savings in fuel and emissions. Thus,
gration of the PSA unit in the hydrogen Further, in order to have an exhaus- realistic and long-term cost of feed, fuel,
plant based on high performance adsor- tive analysis of the furnace behaviour in export steam and operational philoso-
bents, automatic purity control, better terms of fluid dynamics of combustion phy are necessary to tailor a flow
stability of the purge gas circuit and and heat transfer, advanced computa- scheme that best suits specific needs.
smoother reduced-bed operation. tional fluid dynamics (CFD) modelling
is employed to assess the performance Cogeneration
Reformer design of the reformer under different geome- Fuel and power costs as well as power
The steam reforming process is carried tries and operating conditions. These reliability dictate the feasibility of inte-
out in tubular reactors that are highly techniques are used not only for design- grating a power generation unit into a
endothermic and catalytically con- ing new reformers but also to evaluate hydrogen plant. The steam generation
trolled. Heat is supplied by the burners the performance of existing reformers can be maximised in the reformer and
in the furnace box and transferred to for revamping and/or troubleshooting. further increased through the auxiliary
the catalyst tubes mainly by radiation. boiler for power generation in a steam
The SMR is essentially a fired reactor Steam philosophy turbo-generator (STG), especially in the
consisting of a multitude of catalyst- Specific energy efficiency is defined as case of low-credit fuels in the refinery.
filled tubes located in a firebox. It the ratio of total heat output to heat The hydrogen plant not only
involves simultaneous heat and mass input. For a hydrogen plant, it is the becomes self-sufficient in power but can
transfer in a non-adiabatic catalytic sys- sum of heating value of product hydro- also export power to improve the overall
tem, thus its design incorporates com- gen and the enthalpy of export steam, economics depending upon specific site
plex interactive thermodynamic and divided by the heat of combustion of conditions.
kinetic models based on zonal heat feed and fuel. In a PSA-based hydrogen For large hydrogen plants, gas-tur-
transfer for rigorous simulation of both plant, the purification does not require bine based power integration can also
process side as well as combustion side. any heat input, apart from the fact that be very promising based on fuel-power
The models need to be extensively vali- PSA purge gas-firing requires some extra strategies, particularly in places having
dated and reconciled against the field fuel to heat up its inerts content (main- power shortage. The cogeneration
data and feedback from operating ly CO2). These factors result in higher schemes can be optimised either on
reformers. Typical layout for a top-fired amount of export steam. combined-cycle or using gas turbine
reformer is shown in Figure 3. Export steam philosophy is impor- exhaust (GTE) as combustion air in the
Based on the technological advances tant in establishing the specific efficien- reformer.
in high temperature metallurgy, the cy of the hydrogen plant. A plant
microalloys have permitted higher design could have the least feed plus Environmental aspects
severity steam reforming in terms of fuel, based on a minimised amount of Though hydrogen usage in refineries is
higher outlet temperature and/or high- export steam and still have higher oper- driven by environmental regulations on
er pressure together with higher heat ating costs, if the steam is credited the transport fuels, the hydrogen plant
flux, while respecting reliability. equivalent or better than the fuel value. itself also needs to comply with the stip-
Though much higher reformer outlet Typical net specific energy efficiencies ulated environmental protection. It
temperatures (say, above 900ºC) tend to (based on feed + fuel – export steam) lie usually entails:
3
offer slightly improved efficiency, they between 3.1–3.5 Gcal/kNm H2 — Specific limits on NOx emissions in
carry related concerns on the allowable (340–380Btu/scf) on LHV basis. the fluegas, which can be achieved using
metal temperature limits, material creep In cases where there is no effective the advanced (ultra) low-NOx burner
and potential metal dusting, despite use or outlet for additional steam, the designs based on fuel/air staging etc; for-
advances in the alloy materials based on amount of export steam needs to be tunately, for hydrogen plants, the NOx
special additives as well as coating of minimised. In such designs, the fired level is inherently reduced due to the
metal surfaces (such as aluminising) duty of the reformer needs to be use of low-caloric purge gas as the pri-

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mary fuel with its high CO2 content
— Minimisation of plant effluent
streams and safe disposal and release of
undesired component streams, includ-
ing fugitive emissions.
With spent catalyst handling and dis-
posal, there are now several specialised
companies who provide services for
unloading, collection and transporta-
tion of spent catalysts and possible
residual value based on their metal (Ni)
content. Sacrificial catalysts like ZnO
can also be disposed of as land-dump.
Design optimisation
Each hydrogen plant design is usually
optimised through evaluation of several
cases for the flow sheet optimisation in
terms of selecting the process route and
steps, followed by optimisation of the
operating conditions and process vari-
ables for the selected flow sheet. To con-
duct such an exercise effectively,
following reliable information is
required for the specific plant in ques-
tion unit price of feed, fuel and power,
credit (and limit) of export steam and
economic pay-back criteria for incre-
mental investment.
In several cases, some specific
requirements and/or criteria can influ-
ence the plant configuration and design
selection, such as:
— Extent of environmental require-
ments
— Potential future capacity demand
— Reliability, or otherwise, of available
power supply and extent of desired
steam-power synergy
— Integration with other units in terms
of feed and utilities, as well as backup or
alternative feedstocks
— Plot space constraints.
Flow sheet optimisation
For the optimisation of the hydrogen
plant flow sheet, the following options
are generally evaluated, as applicable
for the economic analysis:
— Direct reforming v/s with pre-reform-
ing (especially for liquid feedstocks)
— Level of shift conversion – high tem-
perature (HT) only or HT + low temper-
ature (LT) shift or sometimes medium
temperature (MT) shift
— Combustion air preheat (yes/no; and
if yes, the level of preheat)
Combustion air preheat and its level
is a function of desired export steam
and the cost of fuel. By preheating com-
bustion air, fired duty in terms of the
fuel LHV decreases due to the heat recy-
cle from air, and the heat available for
generation of steam is substantially
reduced. This is primarily due to
reduced firing and secondarily due to
the heat recovery shift from steam gen-
eration to air preheating.
In the absence of a target for flow rate
REFINING
of export steam, the additional invest-
ment in an air preheater system is eval-
uated against the saving in fuel
consumption.
Often, refinery hydrogen plants
require minimising the export steam
against fuel savings. Hence, the level of
combustion air preheat has risen over
the recent years up to 550ºC. This
necessitates the use of a two-stage air
preheater with an economiser boiler in
between, to obtain the proper heat
recovery approach and integration in
the convection section.
The consequences of higher levels of
air preheat are towards selection of
proper burner design, along with a
greater need for low-NOx features of fuel
or air staging, since hotter combustion
air causes higher levels of NOx in the
fluegas. Also, proper design provisions
are required for covering the cold-end
corrosion of the air preheater in cases of
extreme range of ambient temperatures
and/or high sulphur level in the make-
up fuel.
Optimisation
Based on the selected flow sheet and
case-specific data, a sensitivity analysis
is conducted on the major process
parameters. This in turn determines the
hourly operating cost as well as the
incremental capital investment in the
plant to ensure overall economics with-
in the given evaluation criteria. The
variables assessed are usually the S:C
ratio, reformer outlet temperature and
pressure.
The S:C ratio is set at a level above a
minimum that prevents coking in the
radiant tubes. For natural gas-based
plants, the S:C ratio ranges between
2.7–3.0, while for naphtha-based plants
it is 3.0–3.5, depending upon the quality
of naphtha.
Reformer outlet temperature deter-
mines (for a fixed S:C ratio) the
methane slip, which indirectly relates
to the feed consumption. The outlet
temperature also affects the reformer
tube design temperature and therefore
its wall thickness. Reformers in hydro-
gen plants are designed to operate at
outlet temperatures typically ranging
from 840 to 920ºC. Thus, the optimisa-
tion of this parameter is dependant on
the relative price of feed and fuel as well
as reformer mechanical design.
Lower reforming pressures are
favourable for feed conversion as well as
reformer design, but it is established
either on the basis of desired product
hydrogen pressure, or in relation to the
available feed pressure. Typically,
reformer outlet pressure in hydrogen
plants lies between 18–35 barg. When
both feed and product compression are
necessary, reformer outlet pressure is
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P T Q AUTUMN 2003
optimised for minimised overall power
consumption and capital cost with due
consideration to compression staging
and to the fact that generally it is eco-
nomical to maximise feed compression
rather than product hydrogen. In some
borderline cases, ejector systems can be
employed to boost the feed pressure by
2–4 bar using the higher pressure pro-
cess steam as the motive fluid.
Heat recycle
Generation of raw hydrogen from
hydrocarbon feeds involves high tem-
perature processing (irrespective of pro-
cess route). It is logical that the thermal
efficiency of the process is directly relat-
ed to the degree of heat recovered from
the waste heat available within the pro-
cess. It is also logical to claim that any
recycle of the waste heat to the process
itself, compared to shifting it to cold
utility, will improve the net energy effi-
ciency of the process.
In steam reforming technology, few
innovative concepts and developments
have been realised to optimise the heat
integration in terms of recycling of
waste heat to the reforming process.
Apart from the basic objective of
improved efficiency, these advances
need to maintain cost effectiveness
without any compromise on reliability,
safety and operational flexibility. Some
of these concepts are HT heat recycle,
MT heat recycle and LT heat recycle.
Advanced concepts in terms of recu-
perative or regenerative reforming
have been developed to reduce the
duty and size of the reformer as well as
of the related steam system. Few inno-
vative concepts and related mechanical
design have been realised for using the
high level heat of the reformed gas
between 600–900°C for reforming part
of the feed. While improving the ener-
gy efficiency, it also lowers the amount
of excess steam against fuel savings,
apart from reducing the size of the
reformer.
This concept comprises mainly a
heat exchanger type reformer having
catalyst-filled tubes. One of the config-
urations, which is proven and is in
place is the “enhanced heat transfer
reformer” (EHTR). The hot process gas
enters the shell side and mixes with the
gas coming out of the tubes before
flowing up for heat recovery in a so-
called 2 in, 1 out, configuration. This
concept also carries exceptional poten-
tial for plant revamping for achieving a
step increase in hydrogen capacity (up
to 30%), without affecting the existing
reformer or posing limitations on the
steam system.
The MT heat recycle concept qualifies
for the level of pre-reforming, which
utilises waste heat between 400–650°C
 REFINING

in the convection section, which has been already described

earlier.
The LT heat recycle concept typically finds interest in recov-
ering the low-level waste heat of the reformer flue gas in the
range of 150–350°C and upgrading to higher-level heat. It
involves evaporating the hot condensate to process steam by
saturating the hot (desulphurised) dry feed.
Though it tends to overlap with the other options of com-
bustion air or boiler feed water preheating, it allows utilisa-
tion of the process condensate without any treatment or
processing and offers good quality export HP steam, apart
from its increased rate without increased firing.

Advanced process control

Hydrogen plant process control has evolved over the years
from simple pneumatic or semi-automatic control systems
to modern, fully automatic integrated DCS systems, also
involving complex multi-variable control and online plant
optimisation. This advancement has led to improved effi-
ciency, reliability, safety and ease of operation.
The advanced plant control systems often use specific
diagnostic routines as well as simulation models and algo-
rithms for plant optimisation and parametric control. They
can conduct direct data reconciliation and multi-variable
sensitivity analysis based on time-based measured data. Fur-
ther, they can be equipped with a functional decision sup-
port system for providing optimised external set points
against a defined objective function or operational targets
(best feed for minimum operating cost or maximised hydro-
gen production etc).
Also in a multiple feed-based plant, automatic feedstock
changeover systems are often desired/employed, which pro-
vide smooth, faster and reliable feed changeover flexibility
by avoiding operator-induced errors as well as any step
reduction in the production.
Hydrogen technology, though quite matured, carries sev-
eral options and critical aspects for ensuring and enhancing
operational reliability, flexibility and specific efficiency for
each plant design. Thus, it requires a detailed process opti-
misation while applying proven operating conditions and
design severity. Other factors, in terms of environmental
compliance for emissions and minimised effluents, as well as
sophistication of operational control, also become important
in establishing the hydrogen plant design.

This article is based on a paper presented at the AIChE Spring

Meeting, New Orleans, USA, March 2003.

Sanjiv Ratan is director syngas technology at Technip Benelux in

The Netherlands. He is responsible for the technological promo-
tion, development and
consolidation of the hydrogen-syngas product line. He holds a
Bachelor of Technology degree in chemical engineering from the
Indian Institute of Technology, New Delhi. He has over 20 years
of experience and has held various posts in the design, engineer-
ing and state-of-the-art effectiveness of hydrogen-syngas plants.
E-mail: sratan@technip.com

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P T Q AUTUMN 2003