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Module 3 : Liquid Fossil Fuel (Petroleum)
Lecture 24: Hydrotreatment, dewaxing, deasphalting













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Keywords: Hydrodesulphurisation, solvent deasphalting, catalytic dewaxing

Hydrotreatment
Hydrotreatment is the refinery process which involves catalytic conversion and removal of
sulphur, nitrogen, oxygen and metals from petroleum crudes and petroleum fractions at high
hydrogen pressures. Hydrotreatment also includes hydrogenation of unsaturates and
hydrocracking of higher molecular weight compound of petroleum fraction to lower molecular
weight molecules. The increased application of hydrotreating can be ascribed to 1) decreasing
availability of light, sweet crudes and thus increasing fraction of heavy sour crudes that must be
processed, 2) upgrade the feedstocks for catalytic reforming and catalytic cracking, 3) follow
strictly the environmental regulations on sulphur limits in the fuels. Hydrocracking has already
been discussed in Module-3, lecture-5. Here the process including the removal of objectionable
sulphur compounds will be stressed upon. The sulphur removal process in refinery is one of the
most important units, called hydrodesulphurization (HDS). This process is used to meet sulphur
specification of fuels.
Sulphides, disulphides, mercaptans, thiophene and its aromatic derivatives are the major
undesirable sulfur compounds present in the petroleum fractions. Sulfur reduction in petroleum
fuels is gaining importance due to the increasing consciousness about the serious consequences
of burning sulfur-bearing fuels. The U.S. Environmental Protection Agency (EPA) had
constituted new sulfur standards of diesel fuel and gasoline to 30 ppm by 2004 and 15 ppm by
2006, respectively. The Indian government has issued a notification to introduce Euro IV
standards and 50 ppm sulfur fuel in 11 metro cities in April, 2010.
In refinery, HDS is done mainly to gasoline and gas-oil cuts, to meet suphur specification. In
HDS process, feed and hydrogen gas are mixed together and heated to the reaction temperature
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in a furnace and also in a heat exchanger. It is then fed to the reactor where catalyst converts
sulphur compounds to H
2
S, saturates olefins and some aromatics, at the reaction condition. The
aromatics saturation is needed for meeting smoke point specification for kerosene. The catalyst
used is cobalt-molybdenum on alumina, if the main aim is to remove sulphur and saturate
olefins, but nickel-molybdenum on alumina is used when the aim is mainly aromatics saturation.
Hydrogen partial pressure is an important parameter which ranges from 20 to 40 bars, depending
on the type of feedstock. Hydrogenation reactions are exothermic and the catalyst bed
temperature is maintained by external cooling and addition of recycle hydrogen. The operating
temperature varies from 340
0
C at the start of the run to 370
0
C at the end of the run. The
residence time of the feed in the reactor increases with increase in sulphur content. If residence
time is kept constant then with increase in sulphur content, either the catalyst volume or
hydrogen partial pressure should be increased.
Dewaxing
The lube bearing crude contains an appreciable amount of paraffin wax in the lube oil boiling
range. Much of these waxes should be removed from lube oil fraction to attain desired pour point
specification. Two types dewaxing processes are mainly used in refinery:
1. Solvent dewaxing
2. Catalytic hydrodewaxing
Solvent dewaxing is done by utilizing a proper solvent which can successfully remove wax from
the lube oil cut. This process involves the steps: crystallization, filtration and solvent recovery. In
the crystallization step, solvent is added with the feedstock and the diluted feed is chilled at a
temperature where wax components are solidified. The solid wax is filtered to remove it from
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oil. The solvent in the oil is recovered by solvent recovery step using flash distillation and
stripping. The solvent is then recycled. The major solvent dewaxing process used in the refinery
is ketone dewaxing process. Other processes are Di/Me process and propane dewaxing process.
Texaco process and Exxon Dilchill process are the two major ketone dewaxing process. Texaco
process uses a mixture of methyl ethyl ketone (MEK) and toluene as solvent. Suitable solvents in
Exxon process include mixtures of MEK and methyl isobutyl ketone (MIBK), MEK and toluene,
dichloromethane and dichloroethane, propylene and acetone. Preferred solvents are ketones.
Particularly preferred solvents include mixtures of MEK and MIBK and MEK and toluene. Both
these ketone processes involve diluting the waxy feed with solvent and chilling the whole
mixture at a controlled rate to produce slurry. Rotary vacuum filters are used to filter the slurry
and the wax cake produced this way is washed with cold solvent to reduce its oil content. The
cold filtrate is utilized to chill the feed stock and solvent mixture. Solvent is recovered from
diluted oil and wax cake by flash vaporization and recycled to the process.
The dewaxing solvent used in Di/Me process is a mixture of dichloroethane and methylene
dichloride. Propane dewaxing process is almost similar to ketone process with the difference
that, propane is used as the solvent. In this process, high pressure equipment is required and
chilling is to be done in evaporative chiller by vaporizing a portion of propane. Propane
dewaxing produces a better product than ketone process and does not require any crystallizer, but
higher energy requirement is the main demerit of the former one.
Catalytic dewaxing process is less costly than solvent dewaxing process. Catalytic dewaxing or
in other words, selective hydrocracking process has been developed to produce low pour point
lubricating oil base stock. This process is based on reactions of selective hydrocracking of n-
paraffinic hydrocarbons with formation of oils with improved low-temperature properties, fuel
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cuts, and gaseous hydrocarbons (propane-butane). The main outline of the process is
hydrocracking in a reactor containing proprietary catalyst followed by a second reactor
containing a hydrofinishing catalyst to saturate the olefins formed in the first reactor. The base
oils obtained by catalytic dewaxing are having improved viscosity at low temperatures. This is
because of the unique properties of the catalyst used in this process, as it selectively separates
linear paraffins from branched paraffins and does not remove all paraffinic hydrocarbons with a
high melting point. This is the reason of low pour point but a good viscosity property of the base
stock.

Deasphalting
Asphaltenes are the high molecular weight compounds comprising of carbon, hydrogen,
nitrogen, oxygen and sulphur with trace amounts of nickel and vanadium. These are high carbon:
hydrogen ratio molecules, mostly condensed ring hydrocarbons and hetero-atom compounds.
The hydrocarbons are precursor of coke formation in some refinery processes, heteroatom
compounds are responsible for poisoning certain catalysts of the secondary processing and
metals are particularly detrimental to cracking catalysts. Asphaltenes are removed by solvent
extraction process. Solvent deasphalting is essential in production of high-quality conversion unit
(FCC and hydrocracking) feedstocks.
Typically light paraffinic solvents, such as, propane, isobutene, butane and pentane are used in
the solvent deasphalting process. Olefinic solvents may also be used. The removal of asphaltene
from oil depends upon the difference in solubility of deasphalted oil (DAO) and asphaltene in a
particular solvent. Except this, solvent composition, temperature of operation and solvent to oil
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ratio are important parameters for separation. Typical uses of DAO are lube oil base stock,
hydrocracker feed, FCC feed etc.
The feed for deasphalting is either atmospheric residue or vacuum residue. The feed is mixed
with the solvent in the feed-solvent mixer and then this mixture is fed into the top distributor of
the alphaltene separator. More solvent is counter currently introduced into the separator through
the bottom distributor for efficient separation. Solvent does not dissolve asphaltene, but dissolve
the oil into it. Hence, asphaltene is dropped out of the solution and comes through the bottom of
the separator. The DAO/solvent mixture comes out from the top. DAO yield and quality are
primarily dependent on the operating temperature. Higher temperature produces lesser quantity
of DAO, where, lower temperature yields more DAO but quality drops down. The solvent cooler
controls the operating temperature of the separator, and in turn controls the yield and quality of
DAO.
DAO/solvent solution, rich in solvent, is fed to a DAO separator to separate the solvent from
DAO by heating above the critical temperature of the pure solvent. This is a supercritical phase
separation step. After separation, the DAO containing some amount of solvent (in one volume of
DAO, slightly less than one volume of solvent) is sent to a DAO stripper to separate the
remaining solvent. Asphaltene obtained from the asphaltene separator is also associated with
some solvent and is again introduced into an asphaltene stripper to recover the trace solvent.
Superheated steam is used to strip off the solvent from both the components. The striped solvent
vapour along with steam is obtained from the top of the stripper and then condensed. Water and
solvent are separated and solvent is recycled to the process.


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Reference
1. Handbook of Industrial Hydrocarbon Processes, J ames G. Speight, Elsevier, 2011.
2. Modern petroleum technology, Downstream, ed. by Alan G, Lucas, Vol 2, 6
th
edition, IP, J ohn
Wiley & Sons Ltd., 2001.
3. Optimization of oxidative desulfurization of thiophene using Cu/titanium silicate-1 by box-
behnken design, N. J ose, S. Sengupta, J .K. Basu, Fuel, 90 (2), 626632, 2011.
4. Catalytic dewaxing in production of base oils, V. M. Shkol'nikov, N. A. Usakova, and O. S.
Stepuro, Chemistry and Technology of Fuels and Oils, 36(I), 21-24, 2000.