UNIT PROCESSES

ASSIGNMENT

MADE BY :NAME:-E.NITHYA
CLASS:-B.TECH-2
ROLL NO:-U13CH039

QUESTION:-What are the various methods for

the production of hydrogen which are used in
chemical process industries?
Topics are:Steam reforming process
Steam iron process
Partial oxidation
hydrogen by electrolysis of water
Thermal decomposition
By-product from catalytic reforming
Hydrogen from ammonia

PRODUCTION OF HYDROGEN (H2) FROM

HYDROCARBON (HC) FEEDSTOCKS BY
STEAM REFORMING.

INTRODUCTION

Hydrogen use has become more widespread in refineries,

hydrogen production has moved from the status of a hightechnology specialty operation to an integral feature of
most refineries. This has been made necessary by the
increase in hydrotreating and hydrocracking, including the
treatment of progressively heavier feedstocks.

Steam reforming is the dominant method for hydrogen

production. This is usually combined with pressure-swing
adsorption (PSA) to purify the hydrogen to greater than 99
vol %.

REACTIONS INVOLVED

CH4+H2O
CO+H2O
CH4+2H2O

CO+3H2
CO2+H2
CO2+4H2

Ch.E-305 Muhammad Asif Akhtar

FEEDSTOCKS

The best feedstocks for steam reforming are light, saturated,

and low in sulfur; this includes natural gas, refinery gas, LPG,
and light naphtha. These feeds can be converted to hydrogen
at high thermal efficiency and low capital cost.

Many recent refinery hydrogen plants have multiple

feedstock flexibility, either in terms of backup or alternative
or mixed feed.

Automatic feedstock change-over has also successfully been

applied by Technip in several modern plants with multiple
feedstock flexibility.
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NATURAL GAS

Natural gas is the most common hydrogen plant feed, since it meets all
the requirements for reformer feed and is low in cost.
A typical pipeline natural gas contains over 90 percent C1 and C2,
with only a few percent of C3 and heavier hydrocarbons.
It may contain traces of CO2, with often significant amounts of N2.
The N2 will affect the purity of the product hydrogen: It can be
removed in the PSA unit if required, but at increased cost. Purification
of natural gas, before reforming, is usually relatively simple.
Traces of sulfur must be removed to avoid poisoning the reformer
catalyst, but the sulfur content is low and generally consists of H2S
plus some mercaptans.
Zinc oxide, often in combination with hydrogenation, is usually
adequate.

TYPICAL NATURAL GAS

COMPOSITION

REFINERY GAS

Refinery gas, containing a substantial amount of hydrogen, can

be an attractive steam reformer feedstock.

Since it is produced as a by-product, it may be available at low

cost.

Processing of refinery gas will depend on its composition,

particularly the levels of olefins and of propane and heavier
hydrocarbons.

Olefins can cause problems by forming coke in the reformer.

They are converted to saturated compounds in the hydrogenator,
giving off heat. This can be a problem if the olefin concentration
is higher than about 5 percent, since the hydrogenator will
overheat.
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LIQUID FEEDS
Liquid feeds, either
LPG or naphtha, can be
attractive feedstocks
where prices are
favorable. Liquid feeds
can also provide backup
feed, if there is a risk of
natural gas
curtailments.

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PROCESSING STEPS

The generic flowsheet consists of

Feed Pre-treatment

Pre reforming (Optional)

Steam-HC Reforming

Shift Conversion and

Hydrogen Purification By Pressure Swing
Adsorption (PSA).
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Syngas__ steam reforming

Licensor: Uhde GmbH

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Hydrogen Production By Steam

Reforming/PSA.

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Steam Reforming/Wet Scrubbing

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DESCRIPTION
(HYDROGEN PRODUCTION BY STEAM
REFORMING/PSA)

Feed pre-treatment normally involves removal of sulfur,

chlorine and other catalyst poisons after preheating to
350 400C.
DESULFURIZATION:

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DESCRIPTION

(CONTD)

The treated feed gas mixed with process steam is

reformed in a fired reformer (with adiadatic prereformer upstream, if used) after necessary superheating. The net reforming reactions are strongly
endothermic.

Heat is supplied by combusting PSA purge gas,

supplemented by makeup fuel in multiple burners in a
top-fired furnace.

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EFFECT OF OPERATING VARIABLES ON

THE REFORMER

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DESCRIPTION

(CONTD)

Reforming severity is optimized for each specific case.

Waste heat from reformed gas is recovered through steam
generation before the water-gas shift conversion.

Most of the carbon monoxide (CO) is further converted

to hydrogen. Process condensate resulting from heat
recovery and cooling is separated and generally reused in
the steam system after necessary treatment.

The gas flows to the PSA unit that provides high-purity

hydrogen product (up to < 1 ppm CO) at near inlet
pressures.
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EFFECT OF PROCESS VARIABLES ON SHIFT

CONVERSION

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STEAM -IRON PROCESS

The Steam-Iron process is one of the oldest commercial methods for

the production of hydrogen. The process was practised from the early
1900s well into 1930s for supplying small quantities of pure hydrogen to
some industries (e.g., aerial navigation). Later, the technology was
supplanted by the more efficient and economical natural gas reforming
process . However, the interest in the Steam-Iron process has grown in
recent times, due to its simplicity, the high purity of hydrogen
obtained, which is especially important for the use of hydrogen in fuel
cells, the feedstock flexibility and the possibility to use renewable
energy sources in this process. The Steam-Iron process produces highpurity hydrogen by separating the hydrogen production and feedstock
oxidation steps using iron oxides subjected to redox cycles.
Simplistically, the chemistry of the Steam-Iron process involves two
subsequent reactions, as shown schematically.

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PRINCIPLE OF THE STEAMIRON PROCESS.

Reducing gas

(H2,CO,Hydrocarbon)

REDUCTION

Spent gas

REDUCTION
Iron oxide

Iron
OXIDATION

H2

OXIDATION

H2O

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In the reduction step, the iron oxide is treated with a reducing feedstock (such as
hydrogen,

mixtures of hydrogen and CO, and various other fuels), and as a result of the
reaction, the
metal (iron) or a partially reduced oxide is obtained. The second step consists in the
oxidation of the reduced material by means of steam, which decomposes, resulting in
a pure
hydrogen stream (without carbon oxides), while the metal oxide is partially
regenerated and
therefore it can be recycled to the reduction step.
In practice, the process is much more complex due to the presence of various reduced
forms
of iron oxides and the simultaneous ocurrence of a number of feedstock
decompositon/oxidation reactions. A few studies have been devoted to the solid-state
kinetics of the process. Models based on nucleation and growth mechanisms have
been proven to describe both the reduction and oxidation reactions. Furthermore, the
decrease in reactivity of the oxide caused by cyclic operation of the alternative
reduction and
oxidation stages, has been investigated and mathematically modelled .

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On the other hand, in order to improve the long-term stability of the oxide as well as enhance

the rate of reactions, the use of foreign metals (acting as promoters) has been proposed.

Several research groups have been exploring the influence of different metal additives on the

redox properties of iron oxides [6-8]. The use of additives such as Al, Cr or Ce has shown to

prevent the deactivation of the oxide associated with the repetition of reduction and oxidation

cycles. Other metals (such as Rh) improve the oxidation rates at low temperatures. It has

been also considered the combination of two/three promoters with different properties, in the

search for a synergistic effect.

Alternatively, the use of fumed-Fe-dust [9] and mill-scale waste [10] from the steel industry

has been suggested as inexpensive base materials rather than synthesized iron oxides.

One of the advantages of the Steam-Iron process relates to high feedstock feasibility.

Table 1 shows a relation of several reducing gas stream for the Steam-Iron process that

have been proposed and studied by different authors. The use of gas obtained from

gasification or reforming in the reduction step, offers an interesting opportunity for developing

and optimizing the Steam-Iron process in combination with a gasifier or a reformer unit. The

advantage of this integrated process concept is the possibility of enhancing the overall

efficiency of the system, by means of energy recovery and recycling of product stream

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PARTIAL OXIDATION

Partial oxidation (POX) reacts hydrocarbon feed with oxygen at high

temperatures to produce a mixture of hydrogen and carbon monoxide.

CH4 + 1/2O2

CO+ 2H2

Since the high temperature takes the place of a catalyst, POX is not
limited to the light, clean feedstocks required for steam reforming.
Partial oxidation is high in capital cost, and for light feeds it has been
generally replaced by steam reforming. However, For heavier feedstocks
it remains the only feasible method.

In the past, POX was considered for hydrogen production because of

expected shortages of light feeds. It can also be attractive as a disposal
method for heavy, high-sulfur streams, such as asphalt or petroleum coke,
which sometimes are difficult to dispose of.

Consuming all a refinery's asphalt or coke by POX would produce more

hydrogen than is likely to be required. Because of this and the economies
of scale required to make POX economic, hydrogen may be more
attractive if produced as a by-product, with electricity as the primary
product.
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ASPHALT COMPOSITION PARTIAL OXIDATION

FEEDSTOCK

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The asphalt is first gasified with oxygen in an empty refractory-lined

chamber to produce a mixture of CO, CO2 and H2. Because of the
high temperature, methane production is minimal. Gas leaving the
gasifier is first quenched in water to remove solids, which include
metals (as ash) and soot. Metals are removed by settling and
filtration, and the soot is recycled to the gasifier. The gas is further
cooled and H2S is removed by scrubbing with a selective solvent.
Sulfur removal is complicated by the fact that a significant amount
of carbonyl sulfide (COS) is formed in the gasifier. This must be
hydrolyzed to H2S, or a solvent that can remove COS must be used.

Hydrogen processing in this system depends on how much of the gas

is to be recovered as hydrogen and how much is to be used as fuel.
Where hydrogen production is a relatively small part of the total gas
stream, a membrane unit can be used to withdraw a hydrogen rich
stream, This is then purified in a PSA unit. In the case where
maximum hydrogen is required, the entire gas stream may be shifted
to convert CO to H2, and a PSA unit used on the total stream.

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ELECTROLYSIS

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ELECTROLYSIS OF WATER

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The electrolysis of one mole of water produces a mole of hydrogen gas

and a half a mole of oxygen gas in their normal diatomic forms. A detailed
analysis of this process makes use of the thermodynamic potentials and
the first law of thermodynamics. This process is presumed to be at 298K
and atmospheric pressure

By providing energy from a battery, water (H2O) can be dissociated into

the diatomic molecules of hydrogen (H2) and oxygen (O2). This process is
a good example of the the application of the four thermodynamic
potentials (internal energy, U, Helmoltz free energy, F = U-TS; Enthalpy,
H = U+pv and Gibbs free energy, G =U+pv-TS.

The electrolysis of one mole of water produces a mole of hydrogen

gas and a half a mole of oxygen gas in their normal diatomic forms. A
detailed analysis of this process makes use of the thermodynamic
potentials and the first law of thermodynamics. This process is
presumed to be at 298K and atmospheric pressure.

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THERMAL DECOMPOSITION OF WATER

By heating water to over 2,000C, it is broken down into hydrogen and

oxygen. This is considered to be an interesting and inexpensive method of
producing hydrogen directly from solar energy. Research is also being
done on the use of catalysts to reduce the temperature for dissociation.
One central problem is the separation of gases at high temperatures to
avoid recombining. The efficiency factor is uncertain.

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CATALYTIC REFORMING OF
PETROLEUM STOCKS

Considerable hydrogen ,400 to 800cubic feet (11 to 22 cubic

metre)/barrel of feedstock , is produced by petroleum refiners in
catalytic reforming operations. Hydrogen-rich gas from the
reforming operation contains hydrogen sulphide and lowmolecular-weight hydrocarbons. Purification involves only a
caustic wash (to remove hydrogen sulphide ) followed by
refrigeration to condense most of the water and higher
hydrocarbons . The resulting gas is usually further dried by
passing it over a solid adsorbent (eg. Activated alumina) and may
be washed with liquid nitrogen to remove more hydrocarbons.
Although the product (95%hydrogen) is suitable for ammonia
synthesis and was formerly so used , present refining processes
have such large requirements of hydrogen (for hydrodesulphurisation and other uses ) that all or practically all byproduct hydrogen is used on-site and doesnt reach the market.

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FROM AMMONIA BY
DISSOCIATION

For metal treating and hydrogen welding , a

source of mixed gas (75% hydrogen- 25%
nitrogen)is the catalytic cracking of ammonia . In
the process liquid ammonia is vapourised ,
preheated by hot gases from the reaction
chamber , and then passed into an electrically
heated reactor. In the presence of a supported
nickel oxide catalyst , the ammonia may be
cracked at pressures up to 20 psig (350kPa) and
temp. ranging from 900 to 980 deg C.The product
gases may be scrubbed with water to remove
traces to unconverted ammonia , and then
dehydrated to yield a dry gas.
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Since each kilogram of liquid ammonia yield 2.8

cubic metre o dissociated gas containing approx.
2.1 cubic metre of hydrogen and 0.7 cubic metre
of nitrogen , it is claimed that a single 150-lb(68kg) cylinder of liq.ammonia can replace 33
cylinders of hydrogen. Pure nitrogen may also be
obtained by burning out the hydrogen at a cost
comparable to or perhaps lower than cylinder
nitrogen. Although it is not economically feasible
to produce pure hydrogen by this process , the
cracked gas is quite satisfactory for many uses
,particularly in the steel industry in the annealing
process.

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THANK
YOU

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