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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
Sanjiv Ratan

ydrogen plays a foremost role in also setting the ground for some inno- (SMR), partial oxidation and auto-ther-
the various hydroprocessing vative developments. Apart from the mal reforming.
operations within oil refining typical stimulus for better cost effective- These processes differ mainly in the
and is considered as a critical compo- ness and operating efficiency, the major range of applicable feedstocks as well as
nent in determining the type and qual- focus has been towards enhancing plant the basic reactants in terms of steam
ity of the refinery products slate. In fact, reliability, safety and operational flexi- and/or oxygen for producing the raw
the configuration and complexity of a bility, compactness of equipment, ease hydrogen-rich syngas.
refinery is often defined by the extent of operation and, undoubtedly, the gov- Steam reforming (SMR) of hydrocar-
of its usage. The past decade has seen a erning environmental factors. bons (ranging from light natural gas up
remarkable growth in hydrogen to heavy naphtha) has been the pre-
demand for meeting the ongoing envi- Production technologies dominant route for the production of
ronmental regulations for cleaner and Over the years, hydrogen has been raw hydrogen. It has been the most
lighter transportation fuels. mostly produced from hydrocarbon widely employed process and has
In the coming years, several develop- feedstocks ranging from natural gas to remained the technology of choice over
ments are taking shape for paving the coal. A very small portion has been pro- the past five decades, accounting for
way to the so-called hydrogen economy duced from water by electrolysis. For more than 90% of the global hydrogen
in relation to hydrogen-based energy hydrogen generation, plant capacities generation capacity, which is
systems, with keen deliberations going could range from as low as 100Nm /hr attributable to being well-proven, reli-
on for sustainable hydrogen in the to over 220 000Nm /hr (0.1 to 200 mil- able, simple to operate, and which
longer term. lion scfd). In the smaller capacity range, offers significant flexibility in feedstock,
The other major use of hydrogen has hydrogen production by electrolysis of apart from being cost-effective.
been as synthesis gas or syngas (its mix- water or dissociation of ammonia and The basic reactions taking place can
ture with other gases like nitrogen or methanol can be justified and econom- be represented by:
carbon-monoxide) for the manufacture ical based on modular units. CnHm + nH2O → nCO + (n+m/2) H2
of bulk chemicals like ammonia and However, as hydrogen capacities (Endothermic steam reforming; n <7)
methanol and for speciality chemicals increase (above 500Nm /hr), the hydro-
nCO + nH2O = nH2 + nCO2 (Exothermic
like oxo-alcohols, MDI/TDI etc. Further, carbon route generally begins to be
water-gas shift conversion)
hydrogen finds substantial use in the more attractive based on overall eco-
metal industry as a reducing medium in nomics. Moreover, for higher capacities For paraffinic feeds, m = 2n + 2 and only
the production of direct reduced iron (above 5000Nm /h), the modular in the case of methane, the reaction
and steel making. approach becomes attractive. becomes an equilibrium reaction. The
Current global production of hydro- The process for manufacturing net overall reaction is still highly
gen, either in its pure form or as syngas, hydrogen from hydrocarbons (on-pur- endothermic and based on its thermo-
is in the range of 60 million Nm /h, pose hydrogen production) usually con- dynamics, it is favoured by higher steam
which is equivalent to about 55 billion sists of four major sections, including to carbon ratio, higher temperature and
scfd or 130 000tpd. Roughly one-third feed preparation and pre-treatment, lower pressure.
of it is generated as on-purpose hydro- syngas or raw hydrogen generation, Based on the intrinsic need for sub-
gen for refineries and another third is water-gas shift conversion and final stantial heat input and high tempera-
produced (as contained hydrogen) in purification. tures, as well as kinetics-limited
the form of syngas for the chemicals The core section from the point of catalytic space velocities, steam reform-
industry. The remaining is divided (in view of criticality, capital intensity and ing is typically conducted in a tubular
decreasing order) over in-situ hydrogen efficiency relates to the syngas genera- reactor with high level heat input by
produced within the refineries (from tion. Hence it encompasses different fuel firing. It typically employs a fire-
catalytic reforming) and olefins com- processing routes and technology box type reformer containing catalyst-
plexes, reducing gas for metals/steel options whose selection mainly filled tubes through which preheated
industry and the various consumer depends upon available feedstocks and feed-plus-steam flows to produce an
industries like edible fats, textile and utilities, capacity, site-specific condi- equilibrium mixture of hydrogen, car-
pharmaceuticals. tions/requirements and, of course, bon-oxides along with the residual
The emerging needs on hydrogen overall economics. methane and steam.
generation and its management have The major and commercially proven The SMR process, as well as reformer
driven concerted advances in some of processes available for producing (syn- tube integrity, is strongly dependant on
the key areas of hydrogen technology, gas for) hydrogen are steam reforming catalytic activity and stability. Hence,

w w w. e p t q . c o m

proper selection and application of cat-

alysts play an important role in the per-
formance and reliability of the process.
Recycle H2
Partial oxidation (POx) technology is compressor
based on incomplete oxidation of Recycle H2
hydrocarbon, usually using oxygen
with little or no steam: Purge gas fuel
Make-up fuel
CnHm + n/2 O2 → m/2 H2 + nCO HC Hydrogen
feed Shift product
Pre- Pre-
The sub-stoichiometric combustion Reforming PSA
treatment reforming conversion
limits the degree of oxidation of CO (optional)
and H2 to CO2 and H2O, respectively,
thus providing syngas with lower
H2/CO ratios. It is a non-catalytic oper- Export steam
ation, which allows much higher tem- system
peratures and is therefore applicable
particularly for processing heavy-end
feedstocks. 30 400 550 900 400 40 Temperature, °C
Oxygen and hydrocarbon are mixed
in a burner and allowed to react at con-
ditions. The process can use a variety of Figure 1 Generic hydrogen plant flowsheet based on SMR-PSA
feeds ranging from natural gas to heavy
residues within the refinery. To enhance dependent on the oxygen price and quantity of low-grade make-up fuel, the
on-stream reliability, usually more than case-specific economics, especially for feed conversion can be adapted
one train of gasifiers are employed to HyCO production.
improve plant availability. SMR becomes the straightforward Catalyst developments
For heavier feeds, which also tend to choice in the case of non-availability of The hydrogen process based on steam
contain higher levels of sulphur and oxygen and feedstock (up to naphtha). reforming is strongly driven by the cat-
other trace impurities like (heavy) met- In other cases, especially in relation to alytic steps. Hence, proper selection and
als etc, elaborate steps are needed for Hy-CO credits, it could require a performance of catalysts play an intrin-
carbon/slag handling and downstream detailed study to evaluate the overall sically important role in optimisation
processing in terms of H2S and CO2 economics. Generally, factors like econ- and reliability of the process. Also the
removal, as well as process condensate omy of scale, low-grade heavy feed, feedstock flexibility of steam reforming
treatment. Further, since the POx pro- cheap oxygen, credit for CO and added has been widely increased with the
cess is based on high-pressure internal value for captive/export power could application of the pre-reforming step
combustion, it does not call for a large favour POx/ATR in specific cases. Never- upstream from the reformer.
external heat input (except for pre-heat- theless, it is generally acknowledged in Notable improvements have been
ing of the reactant streams). According- the industry that steam reforming is the made in the catalysts applied in hydro-
ly, conventional purification schemes technology of choice for hydrogen pro- gen-syngas plants, mainly to respond to
based on machination routes become duction. the sought-after needs and desired char-
more suitable compared to PSA, to The downstream processing of the acteristics that include:
avoid the purge gas fuel (albeit at low reformed gas primarily proceeds — Higher resistance to poisons and pro-
levels), as well the loss of hydrogen in through the steps of shift conversion cess upsets
purge gas. and hydrogen purification using pres- — Catalyst shapes for higher activity
The economics of hydrogen genera- sure swing adsorption (PSA) and related and lower pressure drop
tion via POx is governed by the price waste-heat recovery plus cooling. PSA — Higher space velocities
and/or availability of oxygen and the technology completely replaces the — Longer operating life
credit for using lower grade (heavier) conventional CO2 removal plus metha- — Broader range of operating condi-
feedstock. For processing of lighter feed- nation route and has been the industry tions
stocks ranging from natural gas to refin- norm for over two decades. It provides — Easier startup (and reduction require-
ery offgas, the POx route can be high purity hydrogen (99.99% or even ments)
relatively simpler, more cost effective higher) in a single system operating at — Better selectivity (reduced formation
and reliable, especially for hydrogen- ambient temperatures and without any of undesired by-products).
carbon monoxide (Hy-CO) production. heat input. And specifically for the reforming
Heat recovery features either direct The steam reforming together with catalysts:
quench or indirect steam generation. PSA purification carries inherent inte- — Better resistance to carbon formation
The auto-thermal reforming (ATR) gration of the back-end and the front- while maintaining activity
process is a sort of combination of POx end through the use of PSA purge gas as — Improved thermal stability and
and SMR in one reactor. The feed hydro- primary fuel in the reformer. Such link mechanical strength
carbon mixed with some steam is par- not only results in the reutilising the — Better fixation of potash in alkalised
tially combusted with oxygen, followed unconverted feed as fuel but offers sig- catalysts (minimised migration)
by steam reforming over the catalyst nificant scope for optimising the level — Increased resistance to excursions on
bed within the same vessel. The heat of of feed conversion without affecting steam and temperature.
combustion is utilised to conduct the hydrogen purity and thus helps in The typical process configuration of a
endothermic reforming reaction to achieving the desired objectives of pro- state-of-the-art hydrogen plant consists
almost complete conversion without cess optimisation, flexibility and relia- of the following process steps (Figure 1):
any external heat input (auto-thermal- bility. Thus, depending upon the — Feed pre-treatment
ly), hence the name. relative pricing of feed and fuel or — Pre-reforming (optional)
The ATR applications are also largely imposed utilisation of any specific — Reforming


— CO Shift conversion
— Purification by PSA
Feed re-treatment reformer
Reforming (also pre-reforming) catalyst, Process steam
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 Desulphurisation
levels (down to <100ppb level) prior to
reforming step. Primary
When using heavier feedstocks (such HC feed reformer
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, Figure 2 Pre-reformer integration
which apart from maximising sulphur
pickup, offer online catalyst ating parameters’ window (mainly level as post steam injection, which also
changeover, thus allowing extended of recycle hydrogen and temperature) helps during transient conditions
continuous cycle on-stream runs. In and their effective control philosophy Incorporation of a pre-reformer
case of quite high concentrations of sul- under various operating cases. More- allows higher reformer inlet tempera-
phur, generally in naphtha feedstocks over, special attention needs to be given tures (up to 650 ºC) without the con-
(up to 1000ppm and over) a pre-desul- for proper transition and control during cern for thermal cracking due to the
phurisation unit is employed in terms capacity and/or feedstock change. absence of the C2+ fraction. Hence, it
of (primary) hydrogenation followed by inherently offers the potential for fur-
thermal stripping for bulk removal of Pre-reforming ther reheating reformer feed, thus shift-
H2S, in order to minimise the recurring Feedstock flexibility in SMR has been ing the reformer radiant heat duty to
cost of ZnO as well as spent catalyst widely enhanced by advances in direct convective mode. This shift can reduce
disposal. reforming catalysts as well as applica- the size of the reformer by 5–15%,
In a refinery environment, several tion of pre-reforming upstream from depending upon the feedstock and the
hydrocarbon streams that do not quali- the reformer. Over recent years, pre- operating conditions for the reheat
fy for cost-effective hydrogen recovery, reforming has acquired increasing potential. Another related advantage is
generally end up in the refinery fuel application in a refinery environment the reduction in steam export against
net. However, after proper techno-eco- for achieving multiple feedstock flexi- fuel savings, which can prove quite
nomic assessment based on their com- bility, from natural gas to captive liquid attractive in some cases.
position (including contaminants), hydrocarbon streams such as LPG and Overall, pre-reforming of naphtha
their available pressure and their quan- naphtha, in an efficient and reliable feed can improve the net thermal effi-
tity, some of these streams can be effec- manner. ciency of hydrogen production by
tively utilised as feedstock for hydrogen Pre-reforming is a low-temperature 1–4%, depending upon the type of feed
production. (approximately 400–550ºC) adiabatic and selected operating conditions.
It can often involve compression, reforming step applied upstream from However, the hourly operating costs are
olefin saturation in combination with the reformer for achieving a variety of more sensitive to the relative price of
hydrogenation of organic sulphur and objectives. To achieve low-temperature export steam against fuel. On the other
chlorine compounds, if any. In the case activity, a highly active catalyst is hand, pre-reforming is an additional
of high levels of unsaturates, a dedicat- required, converting a wide range of the process step and with significant cata-
ed recycle loop is usually applied previously mentioned hydrocarbon lyst life-cycle costs. Hence its applica-
around the hydrodesulphuriser (HDS) feedstocks into a methane-rich gas in tion needs to be evaluated on a
reactor for diluting the inlet stream and the presence of steam. case-to-case basis to ensure overall eco-
eventually to remove the exothermic The pre-reforming operation is the nomics while satisfying specific plant
heat of reaction. However, the econom- net result of two competing equilibrium requirements.
ic attractiveness depends upon the reactions, namely steam reforming A simplified scheme of pre-reformer
added value to the “fuel towards feed” (endothermic), and methanation of integration is shown in Figure 2.
(or savings in the hourly operating cost) hydrogen with carbon oxides (exother- Plants using natural gas as one of the
versus the costs of off-gas conditioning. mic). Hence, the temperature profiles feedstocks have the possibility of on-
In the case of multiple feedstocks, it along the catalyst bed are different for line catalyst renewal by isolating and
becomes critical to define the design different feedstocks depending upon bypassing the pre-reformer, while oper-
basis and operational modes for the the inlet conditions and methane equi- ating on natural gas at reduced capa-
feed pre-treatment. It mainly involves librium. To achieve the required tem- city (~70%). For cases where extended
establishing the controlling and/or perature window for different operating continuous operation is required on
worst-case design rating, required oper- cases, part of the process steam is added heavy (liquid) feed, the twin-reactor


configuration in parallel is applied, ery end-uses. Generally, older hydrogen hand, it suffers from inherent concerns
with one reactor as stand-by. This not plants based on conventional purifica- of susceptibility to higher temperature
only takes away the limitations on the tion route involved the two-stage CO (above 350ºC) based on the larger
continuous operation run through shift conversion based on high temper- exotherm due to one step conversion,
online switching of the exhausted reac- ature (HT) followed by low temperature especially on larger CO loads on heavier
tor, but also offers lower annual catalyst (LT), in order to get down to low levels feedstocks for retaining stable activity.
costs and some operational advantages of CO-slip, which could be handled in Secondly, it tends to have higher
during start-up and shutdown. the downstream methanation step. methanol formation due to favourable
However, later hydrogen plants based kinetics, which ends up in the process
Reforming on PSA purification, mostly employed condensate. Being sensitive to tempera-
Steam reforming of hydrocarbon feeds only HT shift, since the product hydro- ture excursions, it requires extra atten-
is generally limited up to heavy naph- gen purity is largely independent of the tion to design, control and operation,
tha (C7) in view of the catalytic require- CO level in the process gas, and all the especially during transient conditions
ments and the potential carbon CO is removed in the PSA purge gas. of start-up and/or feedstock change.
formation. Direct reforming of multiple The HT shift reactor typically oper- The CO slip from MT shift is lower
and/or heavier feedstocks with widely ates on an inlet temperature of than HT shift, but still reasonably high
differing carbon number (CN) requires 320–350°C for bulk conversion of car- compared to LTS due to much higher
major attention in simulating the car- bon monoxide to hydrogen, with typi- exit temperature as well end-of-run
bon margin, which signifies the depar- cal exotherm of 50–80 C and the approach to equilibrium. Thus, it results
ture from the carbon equilibrium in the corresponding CO-slip between 3–6 only in a marginal net (feed + fuel)
reformer tubes based on thermodynam- vol% (dry) in relation to the inlet reduction of say between 0.3 to <1.0% .
ic and kinetic conditions. steam/gas ratio being between 0.4–0.6.
There is a range of available reform- The newer catalyst formulations have PSA purification
ing catalysts that can achieve the been promoted with some copper, The PSA process is based on the princi-
desired carbon margin through specific which apart from improving the activi- ple of relative diffusion and the fact
combinations of alkalised and non-alka- ty, also helps against the potential Fish- that specific molecular adsorbents are
lised catalyst in order to achieve the er-Tropsch (F-T) side reactions as well as capable of binding or letting through
proper alkali profile and the related cat- the extent of catalyst sintering in rela- different gaseous molecules with differ-
alyst activity. tion to steam/gas ratio. ent affinity, depending upon their par-
Important considerations such as Addition of the LT shift in a hydro- tial pressure, size and polarity.
steam-to-carbon (S:C) ratio, inlet tem- gen plant becomes more of an optimi- Accordingly, the various impurity com-
perature and the applied heat flux need sation decision, mainly in cases where ponents can be adsorbed at a higher
to be addressed for proper design in the feed is more expensive than fuel. As pressure and desorbed by “swinging” to
order to achieve effective and reliable a relatively recent development, medi- a lower pressure.
performance. The reforming process is um temperature (MT) shift catalyst has As such, a PSA operation is a batch
carried out in tubular reactors that are been applied in some of the hydrogen process with the adsorber going
highly endothermic and catalytically plants but there has been limited expe- through various stages of depressurisa-
controlled. Heat is supplied by the rience in view of some of the demerits tion in a fixed cycle time. However, by
burners in the furnace box and trans- in terms of temperature sensitivity v/s using multiple adsorbers on a
ferred to the catalyst tubes mainly by activity and by-product methanol for- sequenced basis, constant on-spec prod-
radiation. mation etc. uct flow is maintained. Commercial
The LT shift reactor operates typically units have normally between four and
Water-gas shift with inlet temperatures of around 12 vessels, depending upon the capacity
CO shift conversion, also commonly 200°C and employing copper-based cat- and desired hydrogen recovery.
known as water-gas shift (WGS) is alyst, which is more sensitive to sulphur Hydrogen is almost non-adsorbed,
applied for increasing hydrogen yield poisoning and thermal stability. In view which gives PSA system the unique
through conversion of residual carbon- of allowable temperature of less than capability of producing very high purity
monoxide to hydrogen and carbon- 250ºC, LT shift needs to be applied hydrogen product of 99.99%+ and on a
dioxide in the presence of steam over downstream of a HT shift converter to pressure close to the feed pressure. The
iron and/or copper-based catalyst. Ther- limit exothermic temperature rise effect of increased H2 purity on hydro-
modynamically, lower operating tem- across the catalyst bed. gen recovery is minimal. However, the
peratures are favourable for shift For larger hydrogen plants, it is some- hydrogen recovery is quite sensitive to
conversion, and thus has the following times justifiable to install a LT shift con- the tail gas pressure, which is usually
impact: verter to improve overall efficiency drawn between 20 to 40KPag, providing
— Reduction in feed rate (better feed and/or operating costs, especially in recoveries between 84–90%, depending
conversion) cases where the fuel is cheaper than upon the number of vessels and pres-
— Increase in makeup fuel (reduced feed. The justification for LT shift is sure equalisations.
heating value of PSA purge gas) plant-specific and needs proper evalua- PSA system offers unmatched opera-
— Additional export steam (exothermic tion in each case based on relative pric- tional flexibility against upstream fluc-
heat). ing of feed, fuel and steam. tuations in terms of feed composition
Over the years, advances and devel- Application of medium temperature and/or flow swings. It retains product
opment efforts in shift catalysts have (MT) shift step allows combining the hydrogen purity as well as recovery up
been in terms of specific performance, HT and LT shift in one step. Another to 30% turndown.
extended activity and operational advantage rests in being copper-based, The PSA systems are very reliable and
aspects, such as resistance to upsets and which allows lower S/C ratios in the versatile, needing very little mainte-
reduced by-products formation. upstream reformer without the con- nance due to absence of moving parts
The CO in the hydrogen product is cerns of catalyst sintering and unde- (except on/off valve stems). On-stream
considered as an undesirable impurity sired F-T side-reactions, typical of factors in excess of 99% have been often
or even as a poison in most of its refin- Fe-based HT shift catalyst. On the other demonstrated. Also, the operating life


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
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:
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-


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


in the convection section, which has been already described

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