HDTB

Sector

The HDTB plant of Digboi Refinery comprises of the following units:

Hydro-treating Unit (HDT)

Hydrogen Generation Unit (HGU)
Sour Water Stripping Unit
Sulphur Recovery Unit
High Purity Nitrogen Unit

Hydro-treating Unit
Introduction
The objective of the Hydrotreating processes is to remove sulphur as well as other
compounds which are undesirable and detrimental to the stability and meeting specifications
of the product with respect to its performance and environment. Such compounds for
example are - unsaturated hydrocarbons, nitrogen from refinery process streams. More
stringent specifications, particularly those related to environment impact, has resulted in
extensive application of hydrotreating processes.
Moreover the catalyst used in the reforming of gasoline to boost octane number can only
handle sulphur in the very low ppm level necessitating hydrotreating of naphtha. The
necessity for hydrotreating of middle distillates (kerosene/gasoil) originates from pressure to
reduce sulfur emissions into the environment. Overall, this situation resulted in an increased
necessity for high sulphur removal capability in many refineries.
Hydrotreating is a term loosely used for a wide variety of processes starting with removal of
sulphur (Hydrodesulphurisation) to mild treatment of lube oils for final finishing and
decolourisation (Hydrofinishing).
In certain conventions Hydrodesulphurisation is treated as a distinct term from milder
form Hydrotreating. (see table below).
Hydrodesulphurisation has been extensively used commercially for treating naphtha as
feedstock for catalytic reformers to meet the very stringent sulphuir specification of less than
1 ppm wt to protect the platinum catalyst. It has also been widely used for removal of sulphur
compounds from kerosine and gasoils to make them suitable as blending components. In
cases where products are from catalytic or thermal crackers, hydrogen treatment is used to
improve product quality specifications like colour, smoke point, cetane index, etc.

Process Description:
For Hydrotreating, two basic processes are applied:

Liquid phase process for kerosine and heavier straight-run, cracked distillates and
vacuum gas oil

Vapour phase process for light straight-run and cracked fractions.

The basic configuration of the process is as follows:

The feedstock is mixed with hydrogen-rich make up gas and recycle gas from the reactor. The
mixture exchanges heat with the reactor effluent and is heated in a furnace. It enters a reactor
loaded with catalyst. In the reactor, the sulphur and the nitrogen compounds present in the
feedstock are converted into hydrogen sulphide and ammonia respectively. The olefins
present are saturated with hydrogen to become di-olefins and part of the aromatics will be
hydrogenated. For hydrogenation of aromatics, a higher pressure is needed in the reactor
compared to the normal operating conditions.
The reactor operating conditions are:

Ttemperatures in the range of 300-380 degrees C

Pressure ranging from 10-20 bar for naphta to 30-45 bar for gasoil.

The catalyst used is normally cobalt, molybdenum and nickel finely distributed on
alumina extrudates. It slowly gets deactivated by coke deposit. It is renewed every 2/3
years. It can be regenerated (by burning off the coke) and reused typically once or
twice before its activity degenerates. Catalyst regeneration is, nowadays, mainly
carried out ex- situ by specialised firms.

The reaction products leave the reactor and, after having been cooled to a low temperature,
typically 40-50 degrees C, enter a liquid/gas separation stage. The hydrogen-rich gas from the
high pressure separation is recycled to combine with the feedstock, and the low pressure offgas stream rich in hydrogen sulphide is sent to a gas-treating unit, where hydrogen sulphide is
removed. The clean gas is used as refinery fuel. The liquid stream is sent to a stripping
column where H2S and other undesirable components are removed, and to a vacumn drier for
removal of water.

Hydrogen Generation Unit

The process involved for conversion of Naphtha or Natural gas to
hydrogen is steam reforming.

Introduction
Steam reforming is a method for producing hydrogen, carbon monoxide, or other useful
products from hydrocarbon fuels such as natural gas. This is achieved in a processing device
called a reformer which reacts steam at high temperature with the fossil fuel. The steam
methane reformer is widely used in industry to make hydrogen. There is also interest in the
development of much smaller units based on similar technology to produce hydrogen as a
feedstock for fuel cells. Small-scale steam reforming units to supply fuel cells are currently
the subject of research and development, typically involving the reforming of methanol, but
other fuels are also being considered such as propane, gasoline, autogas, diesel fuel, and
ethanol.

Production of Hydrogen by steam reforming

Steam reforming of natural gas - sometimes referred to as steam methane reforming (SMR) is the most common method of producing commercial bulk hydrogen. Hydrogen is used in
the industrial synthesis of ammonia and other chemicals. At high temperatures (700 1100
C) and in the presence of a metal-based catalyst (nickel), steam reacts with methane to yield
carbon monoxide and hydrogen.

CH4 + H2O CO + 3 H2
Additional hydrogen can be recovered by a lower-temperature gas-shift reaction with the
carbon monoxide produced, in the presence of a copper or iron catalyst. The reaction is
summarized by:

CO + H2O CO2 + H2
The first reaction is strongly endothermic (consumes heat, Hr= 206 kJ/mol), the second
reaction is mildly exothermic (produces heat, Hr= -41 kJ/mol).

The worldwide ammonia production, using hydrogen derived from steam reforming, was 109
million metric tonnes in 2004.
This SMR process is quite different from and not to be confused with catalytic reforming of
naphtha, an oil refinery process that also produces significant amounts of hydrogen along
with high octane gasoline.SMR is approximately 6575% efficient.

Sour Water Stripping Unit

Introduction
Sour Water is the wastewater that is produced from atmospheric and vacuum crude columns
at refineries. Hydrogen sulfide and ammonia are typical components in sour water that need
to be removed before the water can be reused elsewhere in the plant. Removal of these
components is done by sending the sour water from the process to a stripping tower where
heat, in the form of steam, is applied. The ammonia and hydrogen sulfide contained in the
water is released by the heat and exits the top of the tower.

Process
The ideal pH value for stripping H2S is below 5, since above 5, sulfide is primarily found in
the form of ions (HS- or S-2). Alternatively, efficient ammonia stripping requires a pH above
10 to prevent the formation of ammonium (NH4+) ion that cannot be stripped. Although the
most favorable strategy for sour water stripping is a three step process where two separate
stripper towers are used, one for removing hydrogen sulfide and the other for removing
ammonia, economics usually dictates a compromise. Having only one stripper tower and
using a pH around 8 allows adequate removal of both gases.

There are three distinct processing steps in the sour water stripping process: degasification,
hydrogen (acid-gas) stripping and ammonia stripping. Figure 1 shows only one stripper
column.

During the degasification stage the sour water feed from the plant is cooled and fed to a
degasser where dissolved hydrogen, methane and other light hydrocarbons are removed.
These removed gases are known as sour Gas and are pumped off to the Sulfur Recovery Unit
(SRU). This degassed sour water is pumped into a storage tank that serves to dampen the
flow rate and facilitates removal of entrained oil and solids.

Sulphur Recovery Unit

H2S removed in the Sour Water Stripping process is sent to the sulfur recovery unit (SRU) as
acid gas. SRU recovers H2S as elemental sulfur through the Claus reaction (see the attached
figure). Reactions occur in two stages: the flame reaction stage and the catalytic reaction
stage. The former consists of a high-performance burner, mixing chamber, and heat removing
boiler, while the latter has two to three reactor stages. The sulfur recovery rate of the Claus
process is about 95 to 97%. The tail gas that contains unrecovered sulfur is fed to the tail gas
treating unit (TGT). The recovered sulfur is stored in the sulfur pit and shipped as product
after undergoing a degassing process to remove H2S. The Claus process is an equilibrium
process, and a modified version of it with direct oxidation catalysts stored in the final stage is
called SUPERCLAUS. Since this improved process does not depend on Claus equilibrium, it
can attain a 99% recovery ratio without TGT.

High Purity Nitrogen Unit

The nitrogen generator produces nitrogen gas from atmospheric air using molecular sieves
separation technique. It uses a carbon molecular sieve which has ability to preferentially
remove oxygen from air. Our proprietary technique gets higher efficiency of gas separation.

Nitrogen generator consists of two beds filled with carbon molecular sieves. When
compressed air is passed, Nitrogen comes out as product gas from one bed while other bed is
simultaneously regenerated by depressurization to atmospheric pressure. This process of gas
separation is called "Pressure Swing Adsorption" (PSA). From nitrogen generator gas of
purities from 99% to 99.9999% can be produced. simple PSA unit produces raw nitrogen of
99% purity. By adding purification unit to PSA unit, high purity nitrogen can be produced.