Catalytic Dewaxing

Although included under the separation processes, catalytic dewaxing is actually a low-severity
conversion process involving a selective catalytic cracking of n-paraffins. It refers to the process of
removing the waxy molecules (n-paraffin) from petroleum crude by hydrogenation in presence of a solid
catalyst. Because of removing wax, which are long chain n-paraffins, by chemical reaction, the process is
called dewaxing. The selective cracking of n-alkanes takes place in the pores of molecular sieve catalysts,
called zeolites, with pore openings in the order of 0.6nm, which keep i-paraffins out because of their
larger size due to branching in the hydrocarbon skeleton. This selective cracking increases the ratio of i-
paraffins to n-paraffins in the product and lowers its pour point. The lower is the pour point of an oil, the
lower is the temperature at which it can be used in a fluid form. Hydrogen is introduced along with the
feed to prevent coking on the catalyst surfaces. The cracking of n-paraffins produces distillate fuels such
as gasoline as a by-product from catalytic dewaxing.
Deep Catalytic Cracking

Deep Catalytic Crackin (DCC) is a catalytic conversion technology which uses heavy hydrocarbon
feedstocks, such as vacuum gas oil (VGO), vacuum tower bottom (VTB) or VGO blended with de-
asphalted oil (DAO) to produce light olefins (ethylene, propylene and butylenes), LPG, gasoline, and
middle distillates etc. The technology mainly targets maximizing production of propylene (DCC-I) or
maximizing production of iso-olefins (DCC-II). The process scheme of DCC is similar to that of
conventional FCC consisting of reaction-regeneration, fractionation and gas concentration sections.
Feedstock dispersed with steam is fed to the system, then contacted with the hot regenerated catalyst
either in a riser plus fluidized dense bed reactor (for DCC-I) or in a riser reactor (for DCC-II) and is
catalytically cracked. Reactor effluent proceeds to the fractionation and gas concentration sections for
stream separation and further recovery. The coke deposited catalyst is stripped with steam and
transferred to a regenerator where air is introduced and the coke on the catalyst is removed by
combustion. The hot regenerated catalyst is returned to the reactor at a controlled circulation rate to
achieve the heat balance of the system. The schematic diagram of DCCU reaction-regeneration system is
listed in the figure below.
Crude Distillation

The crude oil distillation unit (CDU) is the first processing unit in virtually all petroleum refineries.
Itdistills the incoming crude oil into various fractions of different boiling ranges, each of which are then
processed further in the other refinery processing units. The CDU is often referred to as the atmospheric
distillation unit because it operates at slightly above atmospheric pressure. Crude oil is sent to the
atmospheric distillation unit after desalting and heating. The purpose of atmospheric distillation is
primary separation of various ‘cuts’ of hydrocarbons namely, fuel gases, LPG, naptha, kerosene, diesel
and fuel oil. The heavy hydrocarbon residue left at the bottom of the atmospheric distillation column is
sent to vacuum distillation column for further separation of hydrocarbons under reduced pressure.
Crude Topping Units

Crude oil contains salts which can be harmful to downstream equipment and must be removed. To
remove the salts, water is mixed with the crude oil and typically heated to temperatures between about
215 o F to about 280 o F and allowed to separate in the desalter. The desalted crude enters another
heat exchanger network. Both heat exchanger networks make use of the vapors of the main column
condenser, the pump-around circuit streams (PA1, PA2 and PA3), and the products that need to be
cooled. Then, the preheated crude enters the furnace, where it is heated to about 340-372 o C (644-700
o F). The partially vaporized crude is fed into the feed region (called flash zone) of the atmospheric
column, where the vapor and liquid separate. The vapor includes all the components that comprise the
products, while the liquid is the residue with a small amount of components in the range of gas oil.
These components are removed from the residue by steam stripping at the bottom of the column.
Products are withdrawn from the side of the column and side strippers are used to help controlling the
composition of light components. In addition, to more effectively remove heat, liquid is extracted at
various points of the column and cooled down to be reinjected at a different position on the column.
Cooling water and sometimes air coolers are used in the heat exchangers PA1, PA2 and PA3, but it is
always more advantageous to have these streams release their heat to the raw crude oil in the heat
exchanger networks (HEN), usually called pre-heating trains.
De-Asphalting

This shows a simplified flow diagram of a propane deasphalting process. As the

first step in deasphalting, residue (feedstock) is mixed with four to eight times
volume of liquid propane. Heavier residua require a higher solvent to residue (S/R
) ratio for effective separation of asphalt. Following the precipitation of asphalt,
DAO and asphalt are separated, and each stream is purified and flashed to
recover and recycle the propane solvent. Independent variables in the
deasphalting process include the solvent used, pressure, temperature, S/R, and
contact time. These variables can be controlled to obtain the optimum
conditions for the desired separation in deasphalting. One of the important
dependent variables in the process is the asphaltene yield. The asphaltene yield
increases with the increasing solvent/residue ratio used in the process. This is
an unusual behavior for solvent extraction because, typically, the yield of an
insoluble fraction would decrease with the increasing quantity of solvent used in
the extraction behavior.
Deep Thermal Conversion

The Deep Thermal Conversion (DTC) process significantly narrows the gap between visbreaking and
coking. The process yields a maximum of distillates by applying deep thermal conversion of the vacuum
residue feed and by vacuum flashing of the cracked residue. High distillate yields are obtained, while still
producing a stable liquid residual product, referred to as liquid coke. The liquid coke, not suitable for
blending to commercial fuel, is used for specialty products, gasification and/or combustion e.g. to
generate power and/or hydrogen.

The DTC process can handle atmospheric or vacuum residues. In the configuration presented here (see
fig. 1) the feed is a vacuum residue, which is charged to the heater (1) and from there to the soaker (2),
where the deep conversion takes place. The conversion is maximized by controlling the operating
temperature and pressure. The cracked feed is then charged to an atmospheric fractionator (3) to
produce the desired products like gas, LPG, naphtha, kero (optional) and gasoil. The fractionator
bottoms are, without further reheat, routed to a vacuum flasher (4), which recovers additional gasoil
and waxy distillate. The residual liquid coke is routed for further processing depending on the outlet.
Desulfurization

Removing sulfur (S) from natural gas and from refined petroleum products (such as gasoline or petrol,
jet fuel, kerosene, diesel fuel, and fuel oils) is widely done by Hydrodesulfurization (HDS) (catalytic
chemical process). Removing the sulfur reduces the sulfur dioxide (𝑆𝑂2) emissions that result from using
those fuels in automotive, residential, industrial furnaces, etc.

Usually, the HDS process converts a number of organo-sulfur compounds to 𝐻2𝑆 and sulfur-free organic
compounds. This can be done through catalytic treatment with hydrogen at elevated pressures,
between 150 and 3000 psi, and elevated temperatures, between 290 and 455 °C, using metal catalysts
such as 𝐶𝑜𝑀𝑜/𝐴𝑙2𝑂3 or 𝑁𝑖𝑀𝑜/𝐴𝑙2𝑂33.
Diesel Upgrading

A process for upgrading diesel oil to produce an upgraded diesel fuel comprising the steps of:

 (a) reacting a diesel oil, having a boiling point at normal pressure of about 300°F to about 700°F,
derived from a petroleum source with an oxidant selected from the group consisting of
nitrogenous oxidizing agents and ozone wherein
o (1) the reacting is to an extent sufficient to increase the cetane number of the diesel oil
obtained in step (a) by at least 5 cetane numbers over the cetane number of the diesel oil
feed to step (a), and
o (2) (i) the reacting is such that when the oxidant is a nitrogenous treating agent, the
amount of oxidant, equivalent on a 100% nitric acid basis, is about 10% or less by weight
of the diesel oil feed to step (a); and
 (ii) the reacting is such that when the oxidant is ozone, the amount of oxidant is
sufficient to achieve an about 10% or greater reduction in the sulfur content of
the reacted diesel oil obtained in step (a) over the diesel oil feed to step (a);
 b) contacting the diesel oil from step (a) above with an extracting solvent, the extracting solvent
o (1) having a dipole moment of about 2 or greater,
o (2) being substantially immiscible with the diesel oil obtained in step (a),
o (3) being a nonhalogenated solvent, and
o (4) excluding amines, which are reactive with the oxidant,

or a mixture of such solvents or a water mixture of such solvents comprising about 50% by weight
or less water; and

 (c) separating the diesel oil from step (b) above from the extracting solvent to recover upgraded
diesel fuel.
Gas Treating – H2S removal

Regenerative solid beds, also known as molecular sieves, remove H2S by adsorption instead of chemical
reaction. They are comprised of aluminosilcate crystalline polymers (zeolites), which strip out polar or
polarizable compounds. While this includes H2S, molecular sieves will also remove CO2, water,
methanol, mercaptanes and sulfides, ammonia, mercury, and aromatics to trace levels. H2S is
preferentially removed over CO2 and allows for selective removal from streams containing both.
Gasoline desulfurization

A catalytic cracked naphtha is desulfurized with minimum loss of olefins and octane. The
naphtha is fed to a first distillation column reactor which acts as a depentanizer or dehexanizer
with the lighter material containing most of the olefins and mercaptans being boiled up into a
first distillation reaction zone where the mercaptans are reacted with diolefins to form sulfides
which are removed in the bottoms along with any higher boiling sulfur compounds. The bottoms
are subjected to hydrodesulfurization in a second distillation column reactor where the sulfur
compounds are converted to H2 S and removed. The lighter fraction containing most of the
olefins is thus not subjected to the harsher hydrogenation conditions of the second reactor