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1.1.1 Background
In the evolution of petroleum industry after crude oil was discovered the first
process that got developed was fractional distillation of crude oil. This physical
separation process since then still remains the key process. Simple distillation,
cannot be applied in refining crude oil. Crude oil consists of many components
with boiling points covering a great range of temperatures. Each finished product
such as motor spirit or kerosene comprises a large number of components with
different boiling points. Each product therefore has a boiling range having an
initial boiling point (I.B.P.) and a final boiling point (F.B.P.). By simple
distillation one cannot avoid considerable overlapping of the boiling ranges of the
fractions. To obtain narrow fractions, fractional distillation using fractionating
columns has to be employed.
When a liquid consists of two components, each of these contributes its own
quotum to the total vapour pressure of the liquid, so that when boiling takes place
the pressure in the still is made up of two parts, one exerted by the vapour of the
first component, the other by the vapour of the second and, since the sum of these
partial pressures of the components is equal to atmospheric, the combined vapours
leave the liquid, that is to say, both of the components are able to evaporate at the
same time.
This can be expressed also by saying that the more valatile substance evaporates
more readily, so that its percentage in the vapour is greater than in the liquid.
Because the evaporated part of the liquid contains a higher percentage of the
lighter component than the original liquid, the remainder will necessarily contain
a smaller percentage. Consequently, the boiling point of the remaining liquid will
be higher than that of the original liquid. This will be true as evaporation goes on,
so that longer the evaportion proceeds the higher boiling point of the remainder of
the liquid. Thus, for such a mixture there is no question of a constant boiling
temperature.
The crude oil which is being pumped to the furnace first passes through heat
exchangers, where it picks up heat from the outgoing vapours and residue. Before
it reaches the furnac, its temperature has risen to, say, 180o C. In the furnace, the
crude oil is heated to 340o -370o C, depending on the crude oil and on the residue
needed. The heated oil leaving the pipe still passes to the fractionating columns,
where the separation into fractions or “cuts” takes place. These columns are long
cylindrical vessels set up on end and fitted with a large number of trays of a
special type.
The mixture of vapour and liquid leaving the pipe still is led in at a point near the
bottom of one of these fractionating columns, where it rises gradually through the
vapour uptakes shown. As it rises it cools and a certain amount condenses on each
tray, until is kept just above the holes in the bubble-cap, so that all the vapour has
to pass through liquid, and at the same time liquid head is not very large in order
to avoid excessive pressure drops. It will be apparent that each tray is a little
cooler than the one below it and that, therefore, lighter and lighter products will
be present on each tray as the vapour passes up the column. As the vapours
bubble through the liquid on these trays, that part of the vapour will condense
which has the same boiling point as the liquid on the tray, and in addition any
light fractions present in the liquid on the tray will be re-evaporated. The
temperature throughout such a column is controlled at the bottom by the
temperature of the crude oil leaving the pipe still, and at the top by pumping back
a certain amount of the material which leave the top of the column after
condensing it (this distillate pumped back is termed “reflux”)
In this way, by controlling the temperature at the top and at the bottom, the
temperature variation throughout is kept under control, so that the temperature of
each tray garies gradually from the bottom of the column to the top. The amount
of liquid which is pumped back to the top of the column can be varied as required,
in order to give the correct temperature at the top of the column, which, in turn,
controls the final boiling point of the gasoline leaving at the top.
Although each tray has the tendency to collect liquid of a small range of boiling
points, yet, on account of the complete range of vapours bubbling through any
one tray, a certain amount of material will condense which has a lower boiling
point than the bulk of the liquid on that tray. It is customary, therefore, to draw
the liquid from a selected tray out of the main column into a small subsidiary
column called a “side stripper” and allow it to flow down through several bubble
trays. While passing over these trays, it meets an upward stream of steam, injected
at the bottom of the stripper, which boils off the lightest components and thus
narrows the boiling range. The vapours thus boiled off, together with the steam,
re-enter the main column.
The heaviest fractions of crude oil requires such high temperatures to evaporate
them that cracking might occur. In order to avoid this, distillation is carried out
under vacuum, thus lowering the boiling point.
For the very light fractions, condensation of the vapours cannot be obtained at
atmospheric pressure and temperature, so that distillation is carried out under
pressure, which increases the boiling point and, consequently, the temperature at
which condensation can be obtained.
The crude oil is first processed through a desalter which is a standard feature in all
crude units. Sodium and Magnesium Chlorides carried in the crude, dissociate as
the temperature of the crude goes up there by releasing HCL in the system. This
leads to corrosion. The crude is therefore, desalted. The crude after being pre-
heated in heat exchangers goes to the preflash vassel. While the flashed vapours
go directly to the primary crude splitter the liquid is heated in the furnace to a
temperature around 250o C before entering this column. Apart from the top reflux
a number of circulating refluxes have been provided which exchange heat with
the crude oil in heat exchangers. The column tops are treated in a hydrotreater
bottoms go to gasoline splitter and top to deethanizer and finally to C3 –C4
splitter.
Kerosene and part of light gas oil is taken out as a side stream. The column
bottom is passed through a furnace, raised to a temperature of around 350o C
before entering the secondary crude splitter operates at slight vacuum. The top
product is the balance of the light gas oil, the sidestream is the heavy gas oil and
the bottom product is the long residue.
1.1.9 Adsorption
Adsorption is employed for about the same purpose as absorption; in the process
just mentioned natural gasoline may be separated from natural gas by adsorption
on charcoal. Adsorption is also used to remove undesirable colours from
lubricating oils, usually employing activated clay. The use of molecular sieves in
separating close boiling components deserves a special mention.
1.1.10 Filtration
Filtration after chilling is the usual method for removal of wax from waxy
distillates. The mixture of wax and adhering oil obtained from the press is frozen
and allowed to warm slowly so that the oil drains (sweats) from the cake thus
further purifying the cake.
1.1.11 Crystallization
1.1.12 Extraction
b) Next follows the step of solvent dewaxing. MEX or MIBK are generally used
as solvents. Filtration after chilling through vacuum filters is the usual route to
Wax removal.
c) Finally the low aromatic content dewaxed oil is subjected to clay treatment or
hydrotreatment, for colour improvement.
When automobile industry was in its infancy, it became obvious that the
production of large quantities of straight run gasoline from crude distillation
would involve production of much larger quantities of residual fuels than the
market could absorb. The demand for gasoline thus spurred on scientists to look
for means of obtaining a higher yield of this product from crude oil. The cracking
process brought the desired solution. Thermal cracking was begun on a
commercial scale in the U.S.A. around the year 1913. Around the year 1946 Fluid
Catalytic Cracking (F.C.C.) process was developed.
- Catalytic cracking
- Hydrocracking
- Naphtha reforming
[a] In a simple refinery, where additional naphtha and gas oil fractions need to be
produced, long residue (i.e. the fraction of crude boiling above about 350o C)
will usually be the feed available for thermal cracking. All or part of this feed
can be cracked to a varying degree of severity in a one or two-stage unit and
with or without a high vacuum unit, depending on a particular situation. Often
feedstock characteristics and product requirements are such that maximum
severity of operation is desirable and possible. A varying degree of severity in
a one or two-stage unit and with or without a high vacuum unit, depending on
a particular situation. Often feedstock characteristics and product
requirements are such that maximum severity of operation is desirable and
possible. A varying degree of sophisticatication is conceivable for product
work-up section. Usually a maximum recovery of gas oil is aimed at and
therefore such units are named thermal gas oil units.
[b] In a complex refinery the straight run flashed distillate (boiling range between
350 and 500o C) is used as feedstock for the fluid catalytic cracker and /or
hydrocracker. The remaining short residue (fraction boiling above approx.
500o C) which invariably constitutes the bulk of the residual fuel oil pool has a
very high viscosity and consequently diluents (cutter stocks), such as gas oil
are needed to blend the short residue to commercial grade fuel oils. The
required amount of gas oil can be appreciable. It can be reduced to a
significant extent by subjecting the short residue to the cracking, which lowers
its viscosity. This operation is usually called visbreaking.
The feed is subjected to a high vacuum distillation before being cracked. The
cracked residues are vacuum flashed to recover more feed for the cracking
stage. A very high conversion can be achieved in this way, because each feed
can be cracked under conditions yields are obtained while maintaining
adequate residue stability. Gas oil yields of about 30% wt. On feed can be
achieved. This scheme is particularly suitable for very light or waxy
feedstocks. A soaker can be applied for the short residue cracking under this
scheme.
1.2.2 Hydrocracking
(a) INTRODUCTION
(b) APPLICATIONS
UOP uses three basic flow schemes: (a) Single-stage, (b) Two-Stage, (c)
Series-Flow; there are many modifications of each but pertinent features are
as follows. The choice of flow scheme depends upon the charge stock, the
desired products and the flexibility that is chosen for the process.
Many units are on stream employing the single stage, scheme. Some convert
naphtha into LPG. Others produce jet fuel diesel fuel and lube oil base
stocks from vaccum gas oil and/or deasphalted oil.
(e) Catalysts
UOP has six different catalysts which used separately and in conjunction
with each other in the three basic flow schemes: various combinations of
catalysts and flow schemes provide wide flexibility of applications.
Available catalyst types are as follows: DHC and HC catalysts, are used in
HC Unibon only. (Unibon is the name given by UOP to its hydrocracking
processes).
(i) DHC
These catalysts have the capacity of hydrocracking vacuum gas oils and
deasphalted oils to maximize distillate, such as jet fuel and diesel fuel, and
also to produce lube oil base stocks. There are two DHC catalysts: DHC-2
and DHC-5; selection depends upon the quality of charge stock and desired
products.
(ii) HC- 8
This catalyst is used in series flow units and has the capability of cracking
heavy gas oil into gasoline in the presence of ammonia, H2 ,S and water. It
can also be used to produce LPG from naphtha.
(iii) HC- 9
(iv) RCD
This catalyst is employed for the direct desulfurization of reduced crudes
wherein minimum hydrocracking is desired.
(v) BOC
This catalyst is employed when it is desired to process vacuum bottoms for
the production of distillable hydrocarbons, such as vacuum gas oil.
The world wide trends are a shift from residual fuels towards middle distillates.
Increased Demand of jet fuel and Diesel oil for road transportation explains the
growing market for middle distillates. While FCC yields high octane gasoline
on the other, it does not produce any jet fuel or kerosene. FCC also produces
heavy cycle oils and clarified oil which can only be blended into furnace oil
pool.
Both the Hydrocracker and the FCC use vacuum gas oil (V.G.O) for feed stock
with certain specified limits for metal contaminants i.e. Nickel and Vanadium
and also Conradson Carbon Residue (CCR) – a property that determines the
extent of Coke formation that will occur. The metal contaminants as well as the
coke reduce the vacuum residue, therefore cannot be easily converted to
distillates and thus goes to the residual fuel oil pool. The only processing routes
available in the past, for the vacuum residues were Visbreaking and thermal
cracking which would yield small quantities of distillates but basically reduce
the viscosity thereby requiring lesser quantities of cutter stock for furnace oil
blending.
Source:
The above report has been extracted from the book ‘Technology in Indian
Petroleum Refining Industry by Department of Scientific & Industrial Research’.