HGU PROCESS

In order to reduce vehicular pollution in the country, Government of India, in consultation with the
Ministry of Petroleum has issued Supreme Court Directives to limit the sulphur level of all diesel and
Motor Spirit fuels sold in the country to certain maximum values.
In order to meet the above directive, all refineries in the country have to produce diesel and MS within
specifications. So H2 is required for Hydro treating reactions in HDT Unit , MSQ and IndAdept G
Unit is met by Hydrogen Generation Unit (HGU) whose Basic Engineering Package has been
provided by Technip Benelux.

 Brief Description of Process

This Design and Operating Manual outlines the design and describes the general principles of
commissioning, start-up, operation and shut-down as well as the safety aspects of the 10,000
TPA Hydrogen Unit at Guwahati, India for Indian Oil Corporation Limited. The hydrogen
unit consists of Desulphurisation, Pre-reforming, Reforming and process gas cooling and
High temperature / Low temperature shift conversion sections to increase the hydrogen
content of the process gas. Purification is done with a PSA Unit. The feedstock to the
Hydrogen unit is LRU off gas** and Straight Run Light Naphtha feed. Purpose of the
hydrogen unit is to supply hydrogen to Hydro treating unit (to meet out the Cetane
specifications in diesel fuels) and MSQU unit (to meet the Octane and aromatic content
specification of gasoline fuels).
Design and operating manuals, drawings and documents provided by the respective process
Licensors for Reformer and PSA units must be referred to and studied, in addition.
Operating instructions provided by the suppliers of equipment such as boilers, compressors,
fans, pumps, etc., should be read in conjunction with this manual.
Numerical values given in this manual are design figures, indicating the range within which
practical values may vary during normal operation. The numerical values are indicative only
and may be changed as per the requirement.

 Process Chemistry in Detail

The Hydrogen Plant is divided into 6 main sections:

1. Feed treatment
2. Pre-reforming
3. Reforming
4. Heat recovery
5. Shift
6. Product recovery, i.e. PSA unit
Some hydrogen is recycled to the feed treatment section to be able to meet hydrogen demand
there and the purge gas from the PSA unit is used as fuel in the reforming section.
 1. Catalyst Poisons

For maintaining long production cycle of hydrogen, time period between two successive
catalyst change outs have to be maximized. This is possible only when feedstocks for the unit
consisting of Naphtha and Process Steam shall be free from poisons. The catalyst poisons
irreversibly damages the active sites on the Catalyst & thereby destroys its activity.
The catalysts used in steam reforming of naphtha are highly selective, extremely active and
very sensitive. Even small levels of poisons in hydrocarbon feed stocks such as sulphur,
chlorine and organ metallic compounds diminish the catalyst activity.

Sulphur

Sulphur is poison for Pre-reforming, Reforming and LT shift catalyst. Any sulphur slipping
from desulphurisation section will be adsorbed by pre-reforming catalyst & reduce its
activity. The desulphurisation section is designed to remove sulphur to a level of <0.1
PPMW.

Chlorine

Chlorine is serious poison to pre-reforming and shift catalyst. LT shift catalyst is especially
very sensitive to chlorine. Many alloy steels are sensitive to chloride induced stress corrosion.
Chloride accelerates the sintering of metal crystallites in catalysts.

Silica

Other possible poison is silica, which comes in contact with the catalyst through process
steam. Silica is poison to pre-reforming and LT shift catalyst. Silica content in process steam
should be less than 0.2 PPM. The limits of silica and total dissolved solids are to protect the
catalysts as well as preheat coils.

2. Steam to Carbon Ratio and Carbon Formation.

The stoichiometric requirement of steam per carbon atom for steam reforming and shift
reactions is 2.0, but it is always maintained higher as carbon forming reactions are promoted
under steam reforming conditions.

The severity of the carbon formation depends on.

1. The feed stocks

2. The operating conditions (steam to carbon ratio, pressure and temperature)
3. The type of reformer design.
4. The catalyst loading.
5. The state of catalyst

Carbon forming reactions are suppressed by using excess steam in steam reformers. In
industrial steam reforming, with adiabatic pre-reformer configuration, carbon deposition can
take place at steam to carbon ratio less than 1.5 or due to overheating of the feed.
The carbon deposition occurs due to the following reactions.
CH4 C+2H2 Methane Cracking

CO+H2 C+H2O CO Reduction

2CO C+CO2 CO Disproportionation

In steam naphtha reformer, cracking of higher hydrocarbons to carbon can also take place.

The risk of carbon formation due to cracking is eliminated in the Reforming with pre
reformer configuration.
The steam to carbon ratio is controlled at the inlet of the reforming section. Three different
steam to carbon ratios can be used to determine the amount of steam that has to be added:
Steam to feed weight ratio: The ratio at the Prereformer inlet of the weight flow of steam to
the weight flow of total hydrocarbon feed.
Steam to carbon ratio: The ratio at the Reformer inlet of the moles of steam to the moles of
carbon (excluding carbon dioxide). The moles of carbon are counted as atoms. Thus one
atom of ethane represents two atoms of carbon.
Overall steam to carbon ratio: The ratio of all steam added to the process gas, to the moles
of carbon (excluding carbon dioxide) present in the feed.
3. Equilibrium

A system is at equilibrium if the rate of forward reaction equals the rate of reverse reaction.
The conversion of reactants to product is not complete at equilibrium for a reversible
reaction.
For the methane reforming reaction the equilibrium constant at the exit of the steam reformer
can be calculated by the equation.

P [CO] P [H2]3
K=
P [CH4] P [H2 O]

The equilibrium concentration at the exit of the steam reformer is function of the exit
pressure and temperature and feed composition to the reformer.

Approach to Equilibrium

The composition of the gas leaving the steam reformer is generally not at equilibrium for the
particular pressure and temperature at the reformer O/L but is actually near the equilibrium.
The approach to equilibrium at the exit of the catalyst bed is the difference between actual
gas exit temperature at the O/L of Reformer and the equilibrium temperature corresponding
to the gas composition and the pressure.
4. Feed Pre-treatment Section
The Nickel based Catalyst used in Pre Reformer will be poisoned by the Sulphur & chlorides
present in the Naphtha. In the feed pre-treatment section Sulphur content in Naphtha is
reduced to < 0.1 ppm.
Feed Hydrogenation / Hydrodesulphurisation
LRU off-gases contain significant amount of olefins in addition to H2S. The light naphtha
contains Mercaptanes as well as traces amounts of heavy metals such as arsenic, lead,
vanadium, copper which are catalyst poisons. The olefins are saturated by hydrogen over the
catalyst in the Hydrogenator. This reaction is highly exothermic which needs proper recycle
loop for keeping the temperature rise under control. The resulting temperature is high
enough for complete conversion of mercaptanes to H2S and for efficient removal of H2S in
the downstream ZnO beds. The impurities are absorbed on the Hydrogenator catalyst, which
is duly considered in its operating life.

Some of typical reactions are shown below. (R stands for a Hydrocarbon radical)
Olefin saturation:
R=R + H2 RH-RH (1)
Hydrogenation of organic sulphur and chlorine compounds to form H2S and HCL:

RSH + H2 RH + H2S (2)

RCl + 1/2 H2 RH + HCl (3)

RISR2 + 2H2 RIH + R2H + H2S (4)

RISSR2 + 3H2 RIH + R2H + 2H2S (5)

C2H5 SH + H2 C2H6 + H2S (6)

C6+H5SH + H2 C2H6 + H2S (7)

CH3S C2 H5 + 2H2 C2H6 + H2S (8)

C2 H5SS C2H5 + 3H2 2C2H6 + 2H2S (9)

C4 H8S + 2H2 C4H10 + H2S (10)

(Tetra hydrothiophene)
C4H4S + 4H2 C4H10 + H2S (11)
(Thiophene)

COS + H2 CO + H2S (12)

Because of the very low levels of sulphur compounds found in most Naphtha feed stocks, any
temperature rise observed across catalyst bed is usually a result of olefin saturation. However,
generally no exotherm in bed is seen, as olefin content of SRN is extremely low.
Feed Desulphurisation and Dechlorination
The chlorides and sulphur are poisons for the downstream pre-reformer and the reformer.
HCI is absorbed on a chlorine guard catalyst bed located above the ZnO beds to avoid
formation of Zinc chloride. The sulphur in form of H 2S is removed in the Desulfurizer
containing zinc oxide. The zinc oxide catalyst will remove hydrogen sulphide to levels <0.1
ppmw. The reactions involved are:
HCl + Na-Aluminate NaCl + H2O (13)
ZnO + H2S ZnS + H2O (14)

5. Prereforming and Reforming

Steam Reforming of Naphtha takes place in two Reactors, Adiabatic Pre-Reformer &
Tubular Reformer. Both Reactors are having Nickel based Catalyst. In the Adiabatic Pre-
Reformer having CRG Catalyst all heavier Hydrocarbons are converted to Hydrogen,
Carbon Monoxide, Carbon Dioxide & Methane. In the Tubular Reformer having a Catalyst
ICI-25-4, ICI-57-4G Hydrogen is produced from Methane & Steam by Reforming.
The reactions taking place in the Pre-reformer and the Reformer are:
CnHm + nH2O nCO + (½m +n) H2 (Endothermic) (15)
CO + H2O CO2 + H2 (Exothermic) (16)
For hydrocarbons with a carbon number higher as one (n>1) the equilibrium for reaction (15)
at the outlet of the Pre-reformer will almost be completely to the CO side thus resulting in
almost complete conversion of C2+. However, based on the competing methanation reaction,
the CO & CO2 formed will get partly converted to methane. For methane, this reaction
represents the equilibrium that will determine the methane content in the stream exit the Pre-
reformer.
The conversion of methane with steam to CO and hydrogen is strongly favoured by a high
temperature, low pressure and high steam ratios. At the Reformer outlet, reaction number
(15) will have approached near equilibrium represented by the ‘approach to methane
equilibrium’.
Reaction number (16) is generally referred to as the water gas shift reaction or simply the
shift reaction. The mixture in the Reformer outlet will be essentially at equilibrium for this
reaction. The conversion of carbon monoxide with water to carbon dioxide and hydrogen is
strongly favoured by a low temperature and a high steam quantity, but is independent of
pressure.

6. Shift Conversion
The gas mixture, which leaves the Reformer, is essentially at equilibrium of the shift
reaction. Further shift conversion is applied at lower temperatures to convert carbon
monoxide to hydrogen. The reactors are operated at the temperatures consistent with the
catalyst stability and design of heat recovery train, in order to optimize the hydrogen yield
from the feedstock.
The principal reaction is:
CO + H2O CO2 + H2 (Exothermic) (17)
The outlet composition of the shift reactors is a function of both the equilibrium temperature
and the catalyst activity. The optimum operation temperature at the inlet of the reactors will
change while the catalyst ages and can be based on CO slip from the reactor. For the High
Temperature Shift Reactor the start of run inlet temperature is 320 oC and can be increased
over the life to 350oC to limit the CO slip. For the Low Temperature Shift Reactor start of
run is at 190oC and over the catalyst life can be increased to 215oC.
In the High Temperature Shift Reactor, a copper promoted iron oxide catalyst is applied. In
the Low Temperature Shift Reactor a copper based catalyst is applied.
In overall case Reaction equilibrium is controlled by the partial Pressure of CH 4, H2, CO &
CO2. The Reforming reactions are strongly Endothermic hence forward reactions are
favoured by high Temperature as well as by low Pressure while the shift reaction is
Exothermic and is strongly favoured by low Temperature and is largely unaffected by
Pressure.
To maximise overall efficiency of the conversion for higher yield of Hydrogen, reformers
are operated at high Temperature and relatively lower Pressure.

7. Pressure Swing Adsorption (PSA)

PSA technology is used to produce very high purity hydrogen at pressure from the reformed
gas. This is achieved by molecular sieves, which adsorb the contaminants and allow the
hydrogen to pass. To regenerate the molecular sieves the adsorber is depressurized. This
releases the contaminants and, after pressurization, the adsorber is ready for reuse. The
contaminants, which are released at low pressure, are collected in the purge gas drum and are
used to meet part of the heat demand of the reformer.
8. Boiler Feed Water Conditioning
Process condensate from the heat recovery train, is recycled for preparation of boiler feed
water and is supplemented by imported demineralised water. The process condensates are
separated at two temperature levels and are fed to the degasifier. The balance requirement of
demineralised water is preheated and fed to Degasifier.
Dissolved gases such as oxygen, carbon dioxide etc. are removed in the Degasifier by
stripping. The stripping is ensured by flash steam from boiler blow down together with HP
steam generated within the unit. There is a chemicals additives unit for oxygen scavenging,
deposit control and pH control.
9. Waste Handling
The waste streams in the process are handled as follows:
- The flue gases from the Reformer are sent to atmosphere via a stack.
- Flammable relieves from safety valves and operational upsets are routed to a flare
header and connected to B.L.
- Blow down from the steam system is flashed and the condensate is cooled before
sending it to the sewer system
- The vent form the Degasifier and other gases/vapours, e.g. steam that also have to
be relieved from the unit in case of an emergency, are vented to the atmosphere in
a safe location.
  Operating Variables

Feed Preparation:
It is required to keep the Reformer catalyst in a reduced condition. Due to the low sulpher
content in the feed, a loss of recycle hydrogen can be accepted for a short time. Therefor a
low alarm indication requires operator action. Sulpher content in the feed gas leaving the
Desulphurizers should be maintained below a maximum of 0.2 ppmw by operating
desulphurizer at 350-360°C. It is preferable to operate below 0.1 ppmw.

Pre-reformer:
A steady flow rate and pressure along with a constant temperature have to be maintained. As
mentioned before, the feedstock should contain less sulpher. It is recommended that catalyst
exposure to steam along is limited to no more than 15 minutes and to steam/hydrogen for no
more than 12 hours. Exposing pre-reformer catalyst to water is extremely damaging to
catalyst. Preheat temperatures to naphtha should not be lower than 440°C. Note that lowering
the steam to feed ratio will raise the pre-reformer inlet temperature, as a result of the reduced
mass flow through the preheat coil.

Steam reforming:
The normal reformer inlet temperature in 630° C. Higher temperatures should be avoided
since they increases the rate of thermal cracking in the inlet system. As increase in the ratio
would favourably affect the steam/feed reforming reaction also resulting higher degree of CO
conversion, reducing load on HT shift reactor. The normal steam to carbon ration(mol/mol)
for normal feed case 2:8:1 and for 100% SRN case is 3:1. At design conditions, the methane
content is reduced to the required level. Catalyst activity will reduce due to presence of
poisons like sulpher, chlorine and arsenic or carbon formation.

High/Low Temperature Shift Conversion:

Normal operating conditions for high temperature shift reactor are:
Pressure inlet: 23.3 kg/cm²g
Temperature inlet: 330 start of run 349 end of run, Outlet: 408 start of run 248 end of run
Normal operating conditions for low temperature shift reactor are:
Pressure inlet: 22.6 kg/cm²g
Temperature inlet: 190 start of run 218 end of run, Outlet: 222 start of run 248 end of run
 Process flow Diagram: