Hydrogen at I On

Ch.
E-305 Muhammad Asif Akhtar 2

Ch.E-305 Muhammad Asif Akhtar 3
11
13
15
19
26
34
Introduction
Mechanism of Catalytic Hydrogenation
Hydrogen Production
Parameters Affecting Hydrogenation
Technologies for Hydrogen Purification
Hydrogenation in Refining Processes
Hydrogenation in Gas Processes

 Hydrogenationis the addition of hydrogen to a
chemical compound.
 Generally, the process involves elevated

temperature and relatively high pressure in the
presence of a catalyst.

Hydrogenation may be either destructive or non-
destructive.
In the former case, hydrocarbon chains are ruptured

(cracked) and hydrogen is added where the breaks have
occurred.
In the latter, hydrogen is added to a molecule that is

unsaturated with respect to hydrogen. In either case, the
resulting molecules are highly stable.

APPLICATION
Hydrogenation yields many useful chemicals, and its use

has increased phenomenally, particularly in the petroleum
refining industry. Besides saturating double bonds,
hydrogenation can be used to eliminate other elements
from a molecule. These elements include:
 Oxygen
 Nitrogen
 Halogens
 Sulfur
2. Cracking (thermal decomposition) in the presence of hydrogen is
particularly effective in desulfurizing high-boiling petroleum fractions,
thereby producing lower-boiling and higher-quality products
REACTION TYPE ILLUSTRATION
† R = alkyl
M = Fe, Ni
A = metals-adsorbing material

3. Oils have been
hydrogenated for
many decades, to
prolong their shelf life
and make the oils
more stable.

Saturation of olefins is irreversible and the saturation
of aromatics is reversible.
 Hydrogenation is generally carried out in the presence of a
catalyst and under elevated temperature and pressure. Noble
metals, nickel and copper type, and various metals and
metal oxides combinations are the common catalysts.
 The catalyst binds both the H2 and the unsaturated substrate and
facilitates their union.
 Pd and Pt are poisoned by sulfur and can only be used in low-

H2S environments
 Gaseous hydrogen is the usual hydrogenating agent.

 Nickel, prepared in finely divided form by reduction of
nickel oxide in a stream of hydrogen gas at about 300°C,
was introduced by 1897 as a catalyst for the reaction of
hydrogen with unsaturated organic substances to be
conducted at about 175°C. Nickel proved to be one of the
most successful catalysts for such reactions.
 The unsaturated organic substances that are hydrogenated

are usually those containing a double bond, but those
containing a triple bond also may be hydrogenated.
 Platinum, palladium, copper metal, copper oxide, nickel

oxide, aluminum, and other materials have subsequently
been developed as hydrogenation catalysts. New catalysts
have helped increase the conversion and yields.

 Inhydrogenation processes, heating of the ingoing
materials is best accomplished by heat exchange
with the outgoing materials.
 It is usually better practice to add all the heat

needed to the materials before they enter the
reactor and then simply have the reactor properly
insulated thermally.
 Hydrogenation reactions are usually exothermic,

so that once the process is started, the problem
may be one of heat removal.
This heat removal is accomplished by allowing the heat
of reaction to flow into the ingoing materials by heat
exchange in the reactor, or, if it is still in excess, by
recycling and cooling in heat exchangers the proper
portion of the material to maintain the desired
temperature.

H H
B Y
H H
C C
A
X

B Y
C C
A
X
H H
H

B
Y
A X
H H
H
C C

B
Y
A X
H H
H
C C

B
Y
A X
H H
C C
H H

 Temperature
 Pressure
 Time
 Liquid- or gas-phase reactions
 Solubility of hydrogen

Liquid- or gas-phase reactions
Decalin
FOUR PROCESSES:
 Thermal Decomposition
 Steam Reforming
 Partial Oxidation
 By Product From Catalytic Reforming
 Hydrogen use has become more widespread in refineries,
hydrogen production has moved from the status of a high-
technology 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 feed stocks.
 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 %.

 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.

 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.
 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.
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.

The generic flowsheet consists of
Feed Pre-treatment
Pre reforming (Optional)
Steam-HC Reforming
Shift Conversion and
Hydrogen Purification By Pressure

Swing Adsorption (PSA).

Hydrogen Production By Steam
Reforming/PSA.

Steam Reforming/Wet Scrubbing

 Feed pre-treatment normally involves removal of sulfur,
chlorine and other catalyst poisons after preheating to
350 – 400°C.

 The treated feed gas mixed with process steam is
reformed in a fired reformer (with adiadatic pre-
reformer upstream, if used) after necessary super-
heating. 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.

 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.

Typical utility requirements for a 50 million SCFD hydrogen
plant feeding natural gas are as follows (no compression is
required).

 Technip has been involved in over 240 hydrogen plants
worldwide.
 Licensor: Technip.

Previous Lecture Review

 Absorption is not adsorption
 absorption: accumulation within (not on) a solid
84
 Terminology
solute
 adsorption: attachment at or near
the interface
 adsorbent: solid to which
adsorption occurs
 adsorbate: solute that adsorbs to
adsorbent
 desorption: release of adsorbate
from adsorbent
 adsorption density: amount of adsorbate
solute adsorbed per surface area
of solid adsorbent
 units of molm-2 or mg cm-2
 represented by q or 
 adsorption isotherm: the
relationship between adsorption
density and solute concentration
(at a given temperature)
85
FEED PHASE PHASE ADDED/CREATED SEPARATING AGENT

Profitability for hydrogen and ammonia plants depends
heavily on the efficiency and reliability of carbon dioxide
(CO2) removal from process gas.
Over the last 30 years, several innovations have evolved
regarding CO2-removal units. New methods have
dramatically increased
• Absorption efficiency
• Reduced CO2 slip to a few parts per million by volume
(ppmv),
• Lowered energy requirements for CO2 regeneration and
mitigated corrosion of plant equipment.

Reactions:
K2CO3 + CO2 + H2O = 2KHCO3
K2CO3 + H2S = KHS + KHCO3
Ch.E-305 Muhammad Asif Akhtar
It uses the Venturi effect of a converging-diverging nozzle to convert
the pressure energy of a motive fluid to velocity energy which creates a low
pressure zone that draws in and entrains a suction fluid. After passing through the
throat of the injector, the mixed fluid expands and the velocity is reduced which
results in recompressing the mixed fluids by converting velocity energy back into
pressure energy.

aMDEA

PSA
Technology
for Hydrogen
Purification

 The PSA process produces a hydrogen stream of four-
nines (99.99%) purity.
 It separates carbon monoxide, carbon dioxide and

unconverted hydrocarbons.
 A bank of adsorbers operates in a cycle where the

adsorbers are rotated through a higher-pressure adsorption
portion, followed by a pressure reduction, which allows
the contaminants to be released from the adsorber.
 The hydrogen gas passes through the adsorber as almost-

pure hydrogen.
A PSA installation consists of four major parts:
 Adsorber vessels made from carbon steel and filled

with adsorbent
 Valves and instrumentation
 Control system which is normally located in a remote
control room
 Mixing drum

A complete pressure-swing cycle consists of the
following five basic steps:
1. Adsorption
2. Cocurrent depressurisation
3. Countercurrent depressurisation
4. Purge at low pressure
5. Repressurisation

Production of any purity hydrogen, typically 90% to
+99.9999 mole%.
Impurities efficiently removed include:

N2, CO, CH4, CO2, H2O, Ar, O2, C2–C8+, CH3OH,
NH3, H2S and organic sulfur compounds.
The technology can also be used to:

Purify CH4, CO2, He, N2 and Cl;
Remove CO2;
Adjust synthesis gas stream composition ratios and
separate nitrogen from hydrocarbons.

 Steam reformer (at any point after the reformer),
 Catalytic reformer net gas
 Refinery purge streams
 Gasification offgases
 Ammonia plant purge gases (before or after the NH3
waterwash)
 Ethylene plant offgases
 Partial oxidation gases
 Styrene plant offgases
 Ethanol plant purge gases
 Coke-oven gas
 Cryogenic purification offgases or other H2 sources.
Feed pressures up to 1,000 psig have been commercially

demonstrated.
 Recovery of H2 varies between 60% and 90%,
depending on composition, pressure levels and
product requirements.
 Typical temperatures are 60°F to 120°F.
 Purity can be +99.9999 mole%.

 Purification is based on advanced pressure swing
adsorption (PSA) technology.
 Purified H2 is delivered at essentially feed pressure, and

impurities are removed at a lower pressure.
 Polybed PSA units contain 4 to 16 adsorber vessels. One

or more vessels are on the adsorption step, while the
others are in various stages of regeneration.
 Single-train Polybed PSA units can have product

capacities over 200 million scfd.

 All systems use advanced proprietary adsorbents and
patented void gas recovery techniques to provide maximum
product recovery.
 Other than entrained liquid removal, no feed pretreatment is

required.
 In addition, all impurities are removed in a single step, and

purities exceeding 90% are obtained irrespective of
impurities.
 Many units presently produce streams with less than one

ppmv impurity from feed concentrations of +40 mole%.

Operation is automatic with pushbutton startup and
shutdown.
After startup, the unit will produce H2 in two to four hours.

Onstream factors in excess of 99.8% relative to unplanned
shutdowns are typical.
Turndown capability is typically 50% but can be even

lower where required.
The units are built compactly with plot plans ranging from
12 ft x 25 ft to 60 ft x 120 ft.
 Units are skid-mounted and modular to minimize
installation costs.
 Material for piping and vessels is carbon steel.
 Control can be via a local or remote-mounted control

panel or by integration into the refinery’s computer
control system.
 Units are designed for outdoor, unattended operation and

require no utilities other than small quantities of
instrument air and power for instrumentation.

More than 700 units are in operation or under construction,
including the world’s first 16-bed system, and the world’s
largest single-train system.
Licensor
UOP LLC.

FEED:
Natural gas, refinery off gases, LPG, naphtha or mixtures.
PRODUCT:
High-purity H2 (typically >99.9%), carbon monoxide
(CO), carbon dioxide (CO2), high-pressure steam and/or
electricity may be produced as separate creditable by-
product.

 The feed is desulfurized (1), mixed with steam and
converted to synthesis gas in steam reformer (2) over a
nickel-containing catalyst at 20 – 40 bar pressure and
outlet temperatures of 800 –900°C.
 The Uhde steam reformer features a well-proven top-fired

design with tubes made of centrifugally cast alloy steel and
a unique proprietary “cold” outlet manifold system for
enhanced reliability.

 A further speciality of Uhde’s H2 plant design is an optional
bi-sectional steam system for the environmentally friendly
full recovery of process condensate and production of high-
pressure export steam (3) with a proven process gas cooler
design.
 The Uhde steam reformer concept also includes a fully pre-

fabricated and modularized convection bank design to
further enhance the plant quality and minimize construction
risks.
 The final process stages are the adiabatic CO shift (4) and a
pressure swing adsorption unit (5) to obtain high-purity H2.

Process options include:
 Feed evaporation
 Adiabatic feed pre-reforming and/or
 HT/LT shift to process, for example, heavier feeds
and/or to optimize feed/fuel consumption and steam
production.
Uhde’s design allows combining maximized process heat

recovery and optimized energy efficiency with
operational safety and reliability.
 The Uhde reformer design is particularly advantageous for
the construction and reliable operation of large-scale
reformers with H2 capacities up to 220,000 Nm3/ h (197
MMscfd) in single-train configurations.
 Uhde offers either standard or tailor-made designs and

applies either customer or own design standards.

Depending on the individual plant concept, the typical
consumption figure for natural gas-based plants (feed + fuel
– steam) can be as low as 3.13 Gcal /1,000 Nm3 (333
MMBtu/MMscf) or 3.09 (329) with pre-reforming.

Recently, Uhde has successfully commissioned large-scale H2 plants for
 SINCOR C.A., Venezuela (2 x 100,000 Nm3/ h or 2 x 90 MMscfd)

 Shell Canada Ltd., Canada (2 x 130,000 Nm3/ h or 2 x 115
MMscfd)
and is presently executing four H2 projects, including H2 plants for
 Neste Oil Oyj (formerly Fortum Oil Oy)

 Finland (1 x 155,000 Nm³/ h or 140 MMscfd) and
 Shell Canada Ltd., Canada, (1 x 150,000 Nm³/ h or 135 MMscfd).
More than 60 Uhde reformers have been designed and constructed

worldwide.

To produce methanol from natural or associated gas
feedstocks using two-step reforming followed by low-
pressure synthesis. This technology is well suited for world-
scale plants to modify ammonia capacity into methanol
production.

 Methanol or methyl alcohol (CH3OH) is a colourless
liquid with a boiling point of 65oC.
 Methanol will mix with a wide variety of organic

liquids as well as with with water and accordingly it is
often used as a solvent for domestic and industrial
applications.
 Methanol is the raw material for many chemicals,

formaldehyde, dimethyl terephphalate, methylamines
and methyl halides, methyl methacrylate, acetic acid,
gasoline etc.
MTBE = methyl tert-butyl ether
DME = dimethyl ether
In recent years methanol has also been used for other
markets such as production of DME (Di-methyl-ether)
and olefins by the so-called methanol-to-olefins process
(MTO) or as blendstock for motor fuels.
The annual production of methanol exceeds 40 million

tons and continues to grow by 4% per year.

The production of methanol from coal is increasing
in locations where natural gas is not available or
expensive such as in China. However, most methanol
is produced from natural gas.
Several new plants have been constructed in areas

where natural gas is available and cheap such as in
the Middle East.
There is little doubt that (cheap) natural gas will

remain the predominant feed for methanol
production for many years to come.
The capacity of methanol plants has increased
significantly only during the last decade. In 1996 a
world scale methanol plant with a capacity of 2500
MTPD was started up in Norway. Today several
plants are in operation with the double of this
capacity.

All commercial methanol technologies feature three
process sections and a utility section as listed below:
 Synthesis gas preparation (reforming)

 Methanol synthesis
 Methanol purification
 Utilities

Synthesis gas is a mixture that contains hydrogen, carbon
monoxide, and carbon dioxide as principal components, and
methane and steam (moisture) as secondary components.
Synthesis gas is also called syngas.
Syngas is typically produced via steam reforming of natural
gas, gasification or partial oxidation of coal, gasification
of biomass, gasification of municipal solid wastes (MSWs).
The typical operating conditions for the methanol synthesis reaction

are 220 to 270°C and 50 to 100 bars
If the feed syngas is free of carbon monoxide, experimental observations
show that the methanol productivity is very low and slowly decreases even
further.
Owing to the total absence of CO, the WGS reaction proceeds in the reverse
direction, i.e., in the direction that will generate more CO.
Considering that the RWGS reaction is a faster reaction than methanol

synthesis reaction, the methanol production rate will have to suffer.
Too high a water concentration in the catalyst pore is detrimental to the

longevity of the catalyst. Therefore, methanol productivity further
decreases.
By the CO hydrogenation mechanism as:
In this case, the WGS reaction proceeds also in the reverse

direction, because of the total lack of carbon monoxide.
According to the CO hydrogenation mechanism, carbon

monoxide is the essential reactant for methanol formation;
however, the only source for this reactant would be coming
from the RWGS reaction, because there is no CO in the feed.
Therefore, the reaction is very seriously limited by lack of the
essential reactant.
Both the mechanisms can explain the situation more or less

properly.
If methanol synthesis is practiced over the Cu/ZnO/Al2O3 catalyst system
using the CO2-free syngas, methanol productivity is also significantly lower
than under normal syngas feed conditions.
According to the CO2 hydrogenation mechanism, the following

stoichiometric equations can be written as:
Owing to the total absence of CO2 in the feed syngas, the WGS reaction
proceeds in the forward direction, resulting in carbon dioxide, which is the
essential reactant for the methanol synthesis reaction utilizing this
mechanism.
Because of the unavailability and limited supply of carbon dioxide, the

principal reaction of methanol synthesis does not proceed properly, resulting
in poor methanol productivity.

The lack of carbon dioxide makes the Boudouard
reaction also proceed in its reverse direction as:
This reaction is responsible for catalyst

deactivation via fouling by carbon deposition.
This may be the reason for the rapid decrease of
methanol productivity.

If CO hydrogenation is taken as the mechanism, the reaction of
CO2-free syngas would be represented by:
The WGS reaction is faster under these conditions and proceeds in the
forward direction as long as there is some H2O in the system.
When there is no CO2 in the feed gas, carbon deposition via Boudouard
reaction can be more active.

Let us assume that the syngas mixture still contains typical amounts of
H2, CO, and CO2.
Then, if we adopt CO2 hydrogenation as the principal reaction for

methanol formation, the reaction system may be described as follows:
The WGS reaction proceeds in the reverse direction, at least in the

beginning, when H2O is totally absent in the feed.
Accordingly, CO2 is the reactant for both the methanol synthesis reaction
via CO2 hydrogenation as well as the RWGS reaction. The two reactions
occur in a competitive manner, thus resulting in a lower productivity of
CH3OH.

In this case, it is rather obvious that the WGS reaction proceeds in the
reverse direction, at least in the beginning, until it reaches WGS
equilibrium.
Other than that, hydrogen is a reactant for both reactions, at least in the
initial stage, and it is not very clear how the final methanol productivity
will be impacted.
The reaction is likely to proceed without much difficulty.

In the design of a methanol plant the three process sections
may be considered independently, and the technology may be
selected and optimized separately for each section.
The normal criteria for the selection of technology are capital

cost and plant efficiency.
The synthesis gas preparation and compression typically

accounts for about 60% of the investment, and almost all
energy is consumed in this process section.
Therefore, the selection of reforming technology is of

paramount importance.

Important properties of the synthesis gas are the CO to
CO2 ratio and the concentration of inerts.
A high CO to CO2 ratio will increase the reaction rate

and the achievable per pass conversion. In addition, the
formation of water will decrease, reducing the catalyst
deactivation rate.
High concentration of inerts will lower the partial

pressure of the active reactants. Inerts in the methanol
synthesis are typically methane, argon and nitrogen.

Most syngas for methanol production is produced by steam
reforming of natural gas. The ideal syngas for methanol
production has a H2/CO ratio of about 2 mol/mol. A small
amount of carbon dioxide (about 5%) increases the catalyst
activity.
A H2/CO ratio lower than 2 mol/mol leads to increased by-

product formation (higher alcohols, etc.), a higher ratio
results in a less efficient plant due to the excess hydrogen
present in the syngas, which has to be purged.
The composition of syngas depends on the feedstock used.

When naphtha is the raw material, the stoichiometry is
approximately right. When methane is used, however,
hydrogen is in excess.

Several reforming technologies are available for
producing synthesis gas:
 One-step reforming with fired tubular reforming

 Two-step reforming
 Autothermal reforming (ATR)

The synthesis gas is produced by tubular steam
reforming alone (without the use of oxygen). This
concept was traditionally dominating.
Today it is mainly considered for up to 2,500 MTPD

plants and for cases where CO2 is contained in the
natural gas or available at low cost from other
sources.

 The synthesis gas produced by one-step reforming
will typically contain a surplus of hydrogen of about
40%. This hydrogen is carried unreacted through the
synthesis section only to be purged and used as
reformer fuel.
 The addition of CO2 permits optimization of the

synthesis gas composition for methanol production.
CO2 constitutes a less expensive feedstock, and
CO2 emission to the environment is reduced.

 The application of CO2 reforming results in a very
energy efficient plant.
 Theenergy consumption is 5–10% less than that of a

conventional plant . A 3,030 MTPD methanol plant
based on CO2 reforming was started up in Iran in
2004.

Methanol — Steam-methane Reforming
Licensor: Haldor Topsøe A/S.

This process features a combination of fired tubular reforming
(primary reforming) followed by oxygen-fired adiabatic
reforming (secondary reforming).
The secondary reformer requires that the primary reformer is

operated with a significant leakage of unconverted methane
(methane slip).
Typically 35 to 45% of the reforming reaction occurs in the

tubular reformer, the rest in the oxygen-fired reformer.
As a consequence the tubular reformer is operated at low S/C

ratio, low temperature and high pressure.

These conditions lead to a reduction in the
transferred duty by about 60% and in the reformer
tube weight by 75 to 80% compared to one-step
reforming.

Methanol— Two-step Reforming
Licensor: Haldor Topsøe A/S.
Light ends: ethers, esters, acetone

and dissolved noncondensable
Ch.E-305 Muhammad Asif Akhtar gases 179
The gas feedstock is compressed (if required),
desulfurized(1) and sent to a saturator (2) where process
steam is generated. All process condensate is reused in the
saturator resulting in a lower water requirement.
The mixture of natural gas and steam is preheated and sent to

the primary reformer (3). Exit gas from the primary reformer
goes directly to an oxygen-blown secondary reformer (4).
The oxygen amount and the balance between primary and

secondary reformer are adjusted so that an almost
stoichiometric synthesis gas with a low inert content is
obtained. The primary reformer is relatively small and the
reforming section operates at about 35 kg/cm2g.

 The flue gas’ heat content preheats reformer feed.
 Likewise, the heat content of the process gas is used to

produce superheated high-pressure steam (5), boiler
feedwater preheating, preheating process condensate going
to the saturator and reboiling in the distillation section (6).
 After final cooling by air or cooling water, the synthesis gas

is compressed in a one-stage compressor (7) and sent to the
synthesis loop (8), comprised of three adiabatic reactors
with heat exchangers between the reactors. Reaction heat
from the loop is used to heat saturator water.

 Steam provides additional heat for the saturator system.
Effluent from the last reactor is cooled by preheating feed
to the first reactor, by air or water cooling.
 Raw methanol is separated and sent directly to the

distillation (6), featuring a very efficient three-column
layout.
 Recycle gas is sent to the recirculator compressor (9) after

a small purge to remove inert compound buildup.

Topsøe supplies a complete range of catalysts that can be used
in the methanol plant. Total energy consumption for this
process scheme is about 7.0 Gcal/ton including energy for
oxygen production.

Total investments, including an oxygen plant, are
approximately 10% lower for large plants than for a
conventional plant based on straight steam reforming.

The two-step reforming lay-out was first used in a
2400 MTPD methanol plant in Norway. This plant
was started up in 1997. A 5000 MTPD plant based
on similar technology was started up in Saudi Arabia
in 2008.
Licensor:
Haldor Topsøe A/S.

ATR features a stand-alone, oxygen-fired reformer.
The autothermal reformer design features a burner, a
combustion zone, and a catalyst bed in a refractory
lined pressure vessel .

 The burner provides mixing of the feed and the oxidant.
 In the combustion zone, the feed and oxygen react.
 The catalyst bed brings the steam reforming and shift

conversion reactions to equilibrium in the synthesis gas
and makes the operation of the ATR soot-free.
 The catalyst loading is optimized with respect to

activity and particle shape and size to ensure low
pressure drop and compact reactor design.
Methanol synthesis gas is characterised by the
stoichiometric ratio (H2 – CO2) / (CO + CO2), often
referred to as the module M. A module of 2 defines a
stoichiometric synthesis gas for formation of
methanol.
The synthesis gas produced by autothermal reforming

is rich in carbon monoxide, resulting in high reactivity
of the gas. The synthesis gas has a module of 1.7 to 1.8
and is thus deficient in hydrogen.

The module must be adjusted to a value of about 2
before the synthesis gas is suitable for methanol
production. The adjustment can be done either
By removing carbon dioxide from the synthesis gas or

By recovering hydrogen from the synthesis loop purge
gas and recycling the recovered hydrogen to the
synthesis gas .
Adjustment by hydrogen recovery can be done either by

a membrane or a PSA unit. Both concepts are well
proven in the industry.
Methanol production by ATR at low S/C ratio. Adjustment
of synthesis gas composition by hydrogen recovery and
recycle. Ch.E-305 Muhammad Asif Akhtar 192
 Natural gas is preheated and desulfurized.
 After desulfurization, the gas is saturated with a mixture of preheated

process water from the distillation section and process condensate in the
saturator.
 The gas is further preheated and mixed with steam as required for the
pre-reforming process.
 In the pre-reformer, the gas is converted to H2, CO2 and CH4.
 Final preheating of the gas is achieved in the fired heater.
 In the autothermal reformer, the gas is reformed with steam and O2.

 The product gas contains H2, CO, CO2 and a small amount
of unconverted CH4 and inerts together with under
composed steam.
 The reformed gas leaving the autothermal reformer

represents a considerable amount of heat, which is
recovered as HP steam for preheating energy and energy for
providing heat for the reboilers in the distillation section.
 The reformed gas is mixed with hydrogen from the pressure

swing adsorption (PSA) unit to adjust the synthesis gas
composition.

 Synthesis gas is pressurized to 5 –10 MPa by a single-casing
synthesis gas compressor and is mixed with recycle gas from
the synthesis loop
 This gas mixture is preheated in the heater in the gas-cooled

methanol reactor.
 In the Lurgi water-cooled methanol reactor, the catalyst is fixed

in vertical tubes surrounded by boiling water.
 The reaction occurs under almost isothermal condition, which

ensures a high conversion and eliminates the danger of catalyst
damage from excessive temperature.
 Exact reaction temperature control is done by pressure control

of the steam drum generating HP steam
 The “preconverted” gas is routed to the shell side of the gas
cooled methanol reactor, which is filled with catalyst.
 The final conversion to methanol is achieved at reduced

temperatures along the optimum reaction route. The reactor
outlet gas is cooled to about 40°C to separate methanol and
water from the gases by preheating BFW and recycle gas.
 Condensed raw methanol is separated from the unreacted

gas and routed to the distillation unit.

 The major portion of the gas is recycled back to the
synthesis reactors to achieve a high overall conversion. The
excellent performance of the Lurgi combined converter
(LCC) methanol synthesis reduces the recycle ratio to about
2.
 A small portion of the recycle gas is withdrawn as purge

gas to lessen inerts accumulation in the loop.

 In the energy-saving three-column distillation section,
low-boiling and high-boiling byproducts are removed.
 Pure methanol is routed to the tank farm, and the

process water is preheated in the fired heater and used
as makeup water for the saturator.

 Energy consumption for a stand-alone plant, including
utilities and oxygen plant, is about 30 GJ/metric ton of
methanol.
 Total installed cost for a 5,000-mtpd plant including

utilities and oxygen plant is about US$350 million,
depending on location.

 Thirty-five methanol plants have been built using
Lurgi’s Low-Pressure methanol technology.
 One Mega Methanol plant is in operation, two are

under construction and three Mega Methanol contracts
have been awarded with capacities up to 6,750 mtpd of
methanol.
 Licensor
Lurgi AG.

 In the methanol synthesis conversion of synthesis gas into
raw methanol takes place. Raw methanol is a mixture of
methanol, a small amount of water, dissolved gases, and
traces of by-products.
 Typical byproducts include DME, higher alcohols, and

minor amounts of acids and aldehydes.
 The methanol synthesis catalyst and process are highly

selective. A selectivity of 99.9% is not uncommon.

The conversion of hydrogen and carbon oxides to
methanol is described by the following reactions:

 The methanol synthesis is exothermic and the
maximum conversion is obtained at low temperature
and high pressure.
 A challenge in the design of a methanol synthesis is to

remove the heat of reaction efficiently and
economically - i.e. at high temperature - and at the
same time to equilibrate the synthesis reaction at low
temperature, ensuring high conversion per pass.

Different designs have been used:
 Quench reactor
 Adiabatic reactors in series
 Boiling water reactors (BWR)

It consists of a number of adiabatic catalyst beds
installed in series in one pressure shell. In practice, up
to five catalyst beds have been used. The reactor feed is
split into several fractions and distributed to the
synthesis reactor between the individual catalyst beds.
The quench reactor design is today considered

obsolete and not suitable for large capacity plants.

 A synthesis loop with normally comprises a number (2-
4) of fixed bed reactors placed in series with cooling
between the reactors. The cooling may be by preheat of
high pressure boiler feed water, generation of medium
pressure steam, and/or by preheat of feed to the first
reactor.
 The adiabatic reactor system features good economy of

scale. Mechanical simplicity contributes to low
investment cost. The design can be scaled up to single-
line capacities of 10,000 MTPD or more.

The BWR is in principle a shell and tube heat
exchanger with catalyst on the tube side.
Cooling of the reactor is provided by

circulating boiling water on the shell side.
By controlling the pressure of the circulating

boiling water the reaction temperature is
controlled and optimized. The steam produced
may be used as process steam, either direct or
via a falling film saturator.

 The isothermal nature of the BWR gives a high
conversion compared to the amount of catalyst installed.
However, to ensure a proper reaction rate the reactor will
operate at intermediate temperatures - say between
240ºC and 260ºC - and consequently the recycle ratio
may still be significant.
 Complex mechanical design of the BWR results in

relatively high investment cost and limits the maximum
size of the reactors.
Thus, for very large scale plants several boiling water
reactors must be installed in parallel.
It is the last section of the plant. The design of this unit
depends on the desired end product. Grade AA methanol
requires removal of essentially all water and by products
while the requirements for fuel grade methanol are more
relaxed.

Aniline is a colorless‚ oily‚ flammable liquid that is
slightly soluble in cold water and infinitely soluble
in alcohol and ether.
Aniline Processes
 Hydrogenation of nitrobenzene‚
 Nitrobenzene reduction with iron filings‚ and
 Ammonolysis of phenol.

The primary aniline production process in the world is
the hydrogenation of nitrobenzene. BASF‚ DuPont‚
ChemFirst (purchased by DuPont in 2002) and Rubicon
use this process in the United States. This technology is
also used by all Western European aniline producers.

 The catalytic gas-phase hydrogenation processes for
nitrobenzene can be carried out using a fixed-bed or a
fluidized bed reactor. Bayer and Allied work with
nickel sulfide catalysts at 300°C to 475°C in a fixed
bed. The selectivity to aniline is more than 99%. The
catalytic activity slowly decreases due to carbon
deposition.
 The catalyst can be regenerated with air at 250°C to

350°C and subsequent H2 treatment.

 The gas-phase hydrogenation of nitrobenzene with a
fluidized-bed catalyst is used in a process from BASF. The
BASF catalyst consists of Cu‚ Cr‚ Ba and Zn oxides on a
support.
 The hydrogenation is conducted at 270°C to 290°C and 1 to

5 bar in the presence of a large excess of hydrogen:
nitrobenzene 9 to 1).
 The high heat of reaction is removed by a cooling system

that is built into the fluidized bed. The selectivity to aniline
is 99.5%‚ and the nitrobenzene conversion is quantitative.
 The catalyst must be regenerated with air periodically.

HYDROGENATION IN REFINNING
AND GAS PROCESSES

REFINERY LAYOUT

 Hydrocracking is a two-stage process combining catalytic
cracking and hydrogenation, wherein heavier feedstock are
cracked in the presence of hydrogen to produce more desirable
products.
 The process employs high pressure, high temperature, a catalyst,

and hydrogen.
 Hydrocracking is used for feedstock that are difficult to process

by either catalytic cracking or reforming, since these feedstock
are characterized usually by a high polycyclic aromatic content
and/or high concentrations of the two principal catalyst poisons,
sulfur and nitrogen compounds.

 Demand for gasoline and diesel is increasing, while the
demand for heavy-oils, such as fuel-oil is declining.
 Refiners are therefore taking more steps to convert

heavy oils into lighter distillates.
 Hydrocracking can significantly improve refining

margins by upgrading low-value products into higher-
value, high-demand products.

 Typical hydrocracking feedstocks include heavy atmospheric and
vacuum gas oils, and catalytically or thermally cracked gas oils.
 These products are converted to lower molecular weight

products, primarly naphtha or distillates.
 Sulphur, nitrogen and oxygen removal and olefin saturation

occur simultaneously with the hydrocracking reaction. Typical
reactor operating conditions are
280 – 475 °C
35 – 215 bar
depending on the feedstock and final products desired. The

reactions consume hydrogen and are highly exothermic.

 Single
stage, once through
hydrocracker
 Singlestage hydrocracker
with recycle
 Two stage hydrocracker

This configuration uses only one reactor and any uncracked
residual hydrocarbon oil from the bottom of the reaction
product fractionation (distillation) tower is not recycled for
further cracking.
For single stage hydrocracking, either the feedstock must first

be hydrotreated to remove ammonia and hydrogen sulfide or
the catalyst used in the single reactor must be capable of
both hydrotreating and hydrocracking.

 This is the most commonly used configuration.
 The uncracked residual hydrocarbon oil from the bottom

of reaction product fractionation tower is recycled back
into the single reactor for further cracking.
 Again, for single stage hydrocracking, either the

feedstock must first be hydrotreated to remove ammonia
and hydrogen sulfide or the catalyst used in the single
reactor must be capable of both hydrotreating and
hydrocracking.
This configuration uses two reactors and the residual
hydrocarbon oil from the bottom of reaction product
fractionation tower is recycled back into the second reactor for
further cracking.
The first stage reactor accomplishes both hydrotreating and

hydrocracking, the second stage reactor feed is virtually free
of ammonia and hydrogen sulfide. This permits the use of
high performance noble metal (palladium, platinum) catalysts
which are susceptible to poisoning by sulfur or nitrogen
compounds.

Basically, catalytic hydrocracking involves three primary chemical
processes:
 Cracking of high-boiling, high molecular weight hydrocarbons

found in petroleum crude oil into lower-boiling, lower
molecular weight hydrocarbons.
 Hydrogenating unsaturated hydrocarbons (whether present in

the original feedstock or formed during the cracking of the high-
boiling, high molecular weight feedstock hydrocarbons) to
obtain saturated hydrocarbons usually referred to as paraffins
or alkanes.
 Hydrogenating any sulfur, nitrogen or oxygen compounds in the

original feedstock into gaseous hydrogen sulfide, ammonia and
water.
Reaction 1:
Addition of hydrogen to aromatics converts them into hydrogenated rings.
These are then readily cracked using acid catalysts.
Reaction 2:
Acid catalyst cracking opens paraffinic rings, breaks larger paraffins into
smaller pieces and creates double bonds.
Reaction 3:
Addition of hydrogen to olefinic double bonds to obtain paraffins.
Reaction 4:
Isomerization of branched and straight-chain paraffins.
 Hydrocracking catalysts consist of active metals on solid,
acidic supports and have a dual function, specifically a
cracking function and a hydrogenation function.
 The cracking function is provided by the acid catalyst support

and the hydrogenation function is provided by the metals.
 The solid acidic support consists of amorphous oxides such

as silica-alumina, crystalline zeolite or a mixture of amorphous
oxides and crystalline zeolite.
 Cracking and isomerization reactions (reactions 2 and 4

above) take place on the acidic support. Metals provide the
hydrogenation reactions (reactions 1 and 3 above).
 The metals that provide the hydrogenation
functions can be the noble
metals palladium and platinum or the base metals
(i.e.,non-noble
metals) molybdenum, tungsten, cobalt or nickel.
 Catalyst cycle life has a major impact on the

economics of hydrocracking. Cycles can be as
short as 1 year or as long as 5 years. Two years are
typical.

 A versatile family of premium distillates technologies
is used to meet all current and possible future premium
diesel upgrading requirements.
 Ultra-deep hydrodesulfurization (UDHDS) process can

produce distillate products with sulfur levels below 10
wppm from a wide range of distillate feedstocks.

High volume yield of ultra-low-sulfur distillate is
produced. Cetane and API gravity uplift, together
with the reduction of polyaromatics to less than 6
wt% or as low as 2 wt%, can be economically
achieved.

The UDHDS reactor and catalyst technology is offered through Akzo
Nobel Catalysts bv.
A single-stage, single-reactor process incorporates proprietary high-
performance distribution and quench internals.
Feed and combined recycle and makeup gas are preheated and contact
the catalyst in a downflow, cocurrent fixed-bed reactor.
The reactor effluent is flashed in a high- and a low-pressure separator.
An amine-absorber tower is used to remove H2S from the recycle gas. In

the example shown, a steam stripper is used for final product recovery.
The UDHDS technology is equally applicable to revamp and
grassroots applications.

Over 60 distillate upgrading units have applied the
Akzo Nobel ultra-deep HDS technology.
Twenty-five of these applications produce, or will
produce, <10ppm sulfur, using UDHDS technology.
 Licensor: Akzo Nobel Catalysts bv.

Reduction of the sulfur, nitrogen and metals content
of naphthas, kerosines, diesel or gas oil streams.
Products
Low-sulfur products for sale or additional processing.

 Single or multibed catalytic treatment of hydrocarbon liquids in the
presence of hydrogen converts organic sulfur to hydrogen sulfide and
organic nitrogen to ammonia.
 Naphtha treating normally occurs in the vapor phase, and heavier oils
usually operate in mixed-phase. Multiple beds may be placed in a
single reactor shell for purposes of redistribution and/or inter bed
quenching for heat removal.
 Hydrogen rich gas is usually recycled to the reactor(s) (1) to maintain

adequate hyrogen- to-feed ratio. Depending on the sulfur level in the
feed, H2S may be scrubbed from the recycle gas.
 Product stripping is done with either a reboiler or with steam. Catalysts

are cobalt-molybdenum, nickel-molybdenum, nickel-tungsten or a
combination of the three.

550°F to 750°F and
400 psig to 1,500 psig reactor conditions.
Yields:
Depend on feed characteristics and product
specifications. Recovery of desired product almost
always exceeds 98.5 wt% and usually exceeds 99%.

Licensor: CB&I Howe-Baker Process and Technology.

Topsøe hydrotreating technology has a wide range of
applications,including the purification of naphtha,
distillates and residue, as well as the deep desulfurization
and color improvement of diesel fuel and pretreatment of
FCC and hydrocracker feedstocks.
Products:
Ultra-low-sulfur diesel fuel, and clean feedstocks for FCC
and hydrocracker units.

Topsøe’s hydrotreating process design incorporates our
industrially proven high-activity TK catalysts with
optimized graded-bed loading and high-performance,
patented reactor internals.
The combination of these features and custom design of

grassroots and revamp hydrotreating units result in
process solutions that meet the refiner’s objectives in
the most economic way.

Typical operating pressures range from
20 to 80 barg (300 to 1,200 psig)

and typical operating temperatures range from
320°C to 400°C (600°F to 750°F).

More than 40 Topsøe hydrotreating units for the
various applications above are in operation or in the
design phase.
Licensor:
Haldor Topsøe A/S.


Hydrogen at I On

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Hydrogen at I On

Uploaded by

Copyright:

Available Formats

Ch.

E-305 Muhammad Asif Akhtar 2

Mechanism of Catalytic Hydrogenation

Parameters Affecting Hydrogenation

Technologies for Hydrogen Purification

Hydrogenation in Refining Processes

Hydrogenation in Gas Processes

 Generally, the process involves elevated

Ch.E-305 Muhammad Asif Akhtar 36

In the former case, hydrocarbon chains are ruptured

In the latter, hydrogen is added to a molecule that is

Ch.E-305 Muhammad Asif Akhtar 37

Hydrogenation yields many useful chemicals, and its use

REACTION TYPE ILLUSTRATION

Ch.E-305 Muhammad Asif Akhtar 39

Ch.E-305 Muhammad Asif Akhtar 40

 Pd and Pt are poisoned by sulfur and can only be used in low-

 Gaseous hydrogen is the usual hydrogenating agent.

 The unsaturated organic substances that are hydrogenated

 Platinum, palladium, copper metal, copper oxide, nickel

Ch.E-305 Muhammad Asif Akhtar 43

 It is usually better practice to add all the heat

 Hydrogenation reactions are usually exothermic,

Ch.E-305 Muhammad Asif Akhtar 45

Ch.E-305 Muhammad Asif Akhtar 49

Ch.E-305 Muhammad Asif Akhtar 50

Ch.E-305 Muhammad Asif Akhtar 51

Ch.E-305 Muhammad Asif Akhtar 52

Ch.E-305 Muhammad Asif Akhtar 53

Ch.E-305 Muhammad Asif Akhtar 54

 Steam reforming is the dominant method for hydrogen

Ch.E-305 Muhammad Asif Akhtar 59

 Many recent refinery hydrogen plants have multiple

 Automatic feedstock change-over has also successfully been

Ch.E-305 Muhammad Asif Akhtar 60

 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

 Traces of sulfur must be removed to avoid poisoning the reformer

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

 Processing of refinery gas will depend on its composition,

 Olefins can cause problems by forming coke in the

Ch.E-305 Muhammad Asif Akhtar 64

Pre reforming (Optional)

Shift Conversion and

Hydrogen Purification By Pressure

Ch.E-305 Muhammad Asif Akhtar 65

Ch.E-305 Muhammad Asif Akhtar 71

Ch.E-305 Muhammad Asif Akhtar 72

Ch.E-305 Muhammad Asif Akhtar 74

 Heat is supplied by combusting PSA purge gas,

Ch.E-305 Muhammad Asif Akhtar 75

 Most of the carbon monoxide (CO) is further converted

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

Ch.E-305 Muhammad Asif Akhtar 77

Ch.E-305 Muhammad Asif Akhtar 81

Ch.E-305 Muhammad Asif Akhtar 82

Ch.E-305 Muhammad Asif Akhtar 83

Ch.E-305 Muhammad Asif Akhtar 86

Ch.E-305 Muhammad Asif Akhtar 88

Ch.E-305 Muhammad Asif Akhtar 96

Ch.E-305 Muhammad Asif Akhtar 98

Ch.E-305 Muhammad Asif Akhtar 101

 It separates carbon monoxide, carbon dioxide and