Petroleum Refinery Prof. Ibtisam Kamal Lec.

Processing Mode

In general, processing mode refers to the way in which feed and product are introduced and
withdrawn from the process. Regarding the distillation process, it occurs in two modes,
continuous distillation and batch distillation.

1. Batch Distillation

Batch Distillation

In batch distillation, the still is filled with liquid mixture and heated. Vapors flows upwards
through the column and condenses at the top. Part of the liquid is returned to the column as
reflux, and the remainder withdrawn as distillate. Nothing is added or withdrawn from the still
until the run is completed.

2. Continuous distillation

Continuous distillation is an ongoing separation in which a mixture is continuously (without

interruption) fed into the process and separated fractions are removed continuously as output
streams.
 Continuous Distillation

Batch Versus Continuous Distillation

Batch stills are more labour-intensive than continuous distillation. After each batch, the still
has to be unloaded and then cleaned out. However, batch distillation can be more flexible and
is to small scale processes. The main reason is production flexibility where different chemicals
are being made in the same equipment.

Despite great flexibility, batch distillation has many disadvantages when compared with
continuous process. Some of them are related to operational difficulties:

It may be difficult to establish when to switch from one cut to another.

It may be difficult to establish optimal reflux ratio, since the pot composition
continuously changes

Making significant changes in process parameters may cause operating instabilities.

The Major Problems That Limit Distillation Processes

There are three major problems that limit distillation processes, they are close-boilers,
distributed keys, and azeotropes:

Close boiler systems include chemicals that boil at temperatures very close to each
other. So many stages of distillation or so much reflux may be required that the
chemicals cannot be separated economically. A good example is separation of nitro-
 chloro-benzenes. Up to 600 theoretical separation stages with high reflux may be
required to separate different isomers.
Distributed keys are systems where some chemicals that we do not want in either the
heavy or the light product boil at a temperature between the heavy and the light
product.
Azeotropic systems are those where the vapor and the liquid reach the same
composition at some point in the distillation. No further separation can occur. Ethanol-
water is a perfect example. Once ethanol composition reaches 95% (at atmospheric
pressure), no further ethanol purification is possible.

Distillation sequence

Stripping systems remove light material from a heavy product.

Rectification systems remove heavy material from a light product.
Fractionation systems remove a light material from a heavy product and a heavy
material from a light product at the same time.
Complex fractionation makes multiple products from either a single tower or a complex
of towers combined with recycle streams between them. A good example of a multiple
product tower is a refinery crude distillation tower making rough cuts of naphtha
(gasoline), kerosene (jet fuel), and diesel from the same tower.
Oil Refinery Production Processes

1. Desalting and Dewatering

Crude oil is recovered from the reservoir mixed with a variety of substances: gases water and
dirt (minerals). If these crude oil contaminants are not removed, they can cause operating
problems during refinery processing, such as equipment plugging and corrosion as well as
catalyst deactivation.
Crude oil is typically produced as a water-in-oil emulsion. The water must be removed (down to
a level of < 1 %) in a process usually called demulsification or dehydration which consists
offorcing the coalescence of water droplets and producing their separation by settling. Water-
in-oil emulsions are stabilized by a wide range of materials that appear naturally in heavy oil,
such as asphaltenes, natural surfactants, and clays.
Water elimination has to meet pipeline specifications) and destabilization of the emulsion is
essential. Demulsification can be achieved by three means: mechanical, electrical, and
chemical. The addition of chemical demulsifiers is the most widely used method.

2. Reforming

Reforming is a process designed to increase the volume of gasoline that can be produced from
a barrel of crude oil. Hydrocarbons in the naphtha stream have roughly the same number of
carbon atoms as those in gasoline, but their structure is generally more complex. Reforming
rearranges naphtha hydrocarbons into gasoline molecules.

Since endothermal reactions are dominant in catalytic reforming reaction, the reforming
process involves three separate catalytic reactors, each one taking place under carefully
controlled temperature and pressure levels. Naphtha is mixed with hydrogen and fed through
each reactor chamber in sequence. Additional hydrogen formed by the catalytic reactors is
recovered and put to use in subsequent reforming and in other processes throughout the
refinery. The other products of reforming are light gases and a high-octane gasoline
blending component called reformate.

The octane rating of reformate is important because it affects the octane rating of the gasoline
we buy at the pump. By controlling the temperature and flow rate of the reformer, refinery
operators can increase the octane rating of the reformate, but that also has the effect of
producing less reformate. The reverse is also true: If demand for high-octane gasoline is lower,
the reformer can be adjusted to produce more reformate with a lower octane rating.

Reforming processes are classified as continuous, cyclic, or semiregenerative depending upon

the frequency of catalyst regeneration. The equipment for the continuous process is designed
to permit the removal and replacement of catalyst during normal operation. The coke laydown
and thermodynamic equibrium yields of reformate are both favored by low pressure operation.

Typical process flow of Catalytic Reformer plant

Benefits Of Catalytic Reforming

Catalytic reforming is a process for converting straight run naphtha into catalytic reformate.
Through this unit, the hydrocarbon molecules are not cracked but their structures are
rearranged to form higher octane aromatics. The reforming plant plays an important role in oil
refinery, that supplies 30-40% of all gasoline demand. Catalytic reformate contains a large
amount of aromatic components, and is the main feedstock in benzene, toluene, xylene (BTX)
production. The reforming plant produces a large amount of hydrogen rich gas, and so the
reforming plant plays as a hydrogen supplier for the hydrodesulfurization plant and
hydrocracking plant in the oil refinery.

Reactions of Reforming

Reforming uses heat, pressure and a catalyst (usually containing platinum).

3. Cracking
Cracking processes break down heavier hydrocarbon molecules (high boiling point oils) into
lighter products such as gasoline and diesel. These processes include:
The purpose of cracking is to produce high demand hydrocarbons:

short-chain alkanes for use in gasoline

alkenes, as a feedstock for a wide range of organic chemicals, including polymers

Cracking is conducted at high temperatures, by two processes

Steam cracking which produces high yields of alkenes

Catalytic cracking in which a catalyst is employed and which produces high yields of
branched and cyclic alkanes

In general, thermal cracking is the process by which the naphtha fraction heats with steam at a
high temperature (about 800C) and high pressure (about 700kPa). This forms a mixture of
straight-chain alkanes and alkenes (mainly ethene) with a small proportion of branched and
cyclic hydrocarbons. Some hydrogen is also produced.
The following equations summarize the overall process of cracking.
Steam cracking is a petrochemical process sometimes used in refineries to produce olefinic raw
materials (e.g., ethylene) from various feedstock for petrochemicals manufacture. The
feedstock range from ethane to vacuum gas oil, with heavier feeds giving higher yields of by-
products such as naphtha.

The most common feeds for steam cracking are

Ethane, propane and butane from natural gas

Naphtha, a mixture of c5 to c10 hydrocarbons, from the distillation of crude oil

Gas oil and residues, also from the primary distillation of oil

Naphtha produced from steam cracking contains benzene, which is extracted prior to
hydrotreating. Residual from steam cracking is sometimes blended into heavy fuels.

Catalytic cracking

By Catalytic cracking, a catalyst is used that allows lower reaction temperatures, and
higher proportion of branched and cyclic hydrocarbons are produced compared to thermal
cracking .
There are three basic functions in the catalytic cracking process:
Reaction: Feedstock reacts with catalyst and cracks into different hydrocarbons;
Regeneration: Catalyst is reactivated by burning off coke; and
Fractionation: Cracked hydrocarbon stream is separated into various products.
The four types of catalytic cracking processes are fixed bed catalytic cracking, fluid bed catalytic
cracking (FCC), moving-bed catalytic cracking, and Thermofor catalytic cracking (TCC).

In Fixed Bed Catalytic Cracking, the catalyst is in the form of small lumps or pellets in layers or
beds in several (four or more) catalyst containing drums called converters
 Fixed bed catalytic cracking

Fluid Bed Catalytic Cracking processes (FCC) are the most widely used and are characterized by
the use of finely powdered catalyst that is moved through the processing unit. Catalyst particles
are of such a size that when aerated with air or hydrocarbon vapor, the catalyst behaves like a
liquid and can be moved through pipes. Vaporized feedstock and fluidized catalyst flow
together into a reaction chamber where the cracking reactions take place.
The feedstock is gas oil which is vaporized and passed through the catalyst (a zeolite) produced
as a fine powder, heated to about 700-800 K in the reactor. It is so fine that it behaves like a
fluid and continuously flows out of the furnace with the cracking products. The temperature,
residence time and the catalyst determine the product proportions. After cracking, the catalyst
is separated from the products, regenerated by burning off deposited carbon in air (900 K), and
subsequently recycled. The catalyst is steam stripped to remove adsorbed hydrocarbons.
 Fluidized Bed Catalytic Cracking

The resulting effluent is processed in fractionators, which separate the effluent based on
various boiling points into several intermediate products, including butane and lighter
hydrocarbons, gasoline, light gas oil, heavy gas oil, and clarified slurry oil.
The relative proportions of the products, can be altered by changing the catalyst and
temperature.
The FCC gasoline must be desulfurized and reformed before it can be blended into finished
gasoline; the light gas oil is desulfurized before blending into finished heating oil or diesel; and
the heavy gas oil is further cracked in either a hydrocracker (using hydrogen and a catalyst) or a
coker. The slurry oil can be blended with residual fuel oil or further processed in the coker.
Features of Catalytic Cracking Processes
Cracking Catalysts Types

Process Variables
The fluidized bed cracking has the following advantages over fixed-bed cracking: 1. Better
contact with the feed and the catalyst, enabling uniform temperature and efficient heat
transfer. 2. The catalyst can be regenerated and used again for the cracking process.

Moving Bed Catalytic Cracking

The moving-bed catalytic cracking process is similar to the FCC process. The catalyst is in the
form of pellets that are moved continuously to the top of the unit by conveyor or pneumatic lift
tubes to a storage hopper, then flow downward by gravity through the reactor, and finally to a
regenerator. The regenerator and hopper are isolated from the reactor by steam seals. The
cracked product is separated into recycle gas, oil, clarified oil, distillate, naphtha, and wet gas.

Thermofor Catalytic Cracking

In a typical thermofor catalytic cracking unit, the preheated feedstock flows by gravity through
the catalytic reactor bed. The vapors are separated from the catalyst and sent to a fractionating
tower. The spent catalyst is regenerated, cooled, and recycled. The flue gas from regeneration
is sent to a carbon monoxide boiler for heat recovery.

Hydrocracking
In hydrocracking, the cracking is carried out with hydrogen at a pressure of 80 atm and a
catalyst of finely divided platinum on silica or alumina. Because excess hydrogen is present no
alkenes are formed, and high proportions of branched alkanes, cycloalkanes and aromatics are
produced which are essential in the formulation of high grade 'green' gasoline. The hydrogen
also decreases the tendency for the hydrocarbons to form finely divided carbon on the catalyst
surface. The reaction products are separated by fractionation.
Hydrocracking is also used to crack heavy gas oils (which have over 20 carbon atoms in the
hydrocarbon molecule) to shorter chain molecules similar to those in naphtha, which can then
be steam cracked to form alkenes.

Hydrocracking Unit
Differences between FCC and Hydrocracking

FCC Hydrocracking