Coking and Thermal

Processes

The ‘‘bottom of the barrel’’ has become more of a problem for refiners because heavier
crudes

are being processed and the market for heavy residual fuel oils has been decreasing.
Historically,

the heavy residual fuel oils have been burned to produce electric power and to supply
the energy

needs of heavy industry, but more severe environmental restrictions have caused many
of these

users to switch to natural gas. Thus when more heavy residuals are in the crude there is
more

difficulty in economically disposing of them. Coking units convert heavy feedstocks into
a solid

coke and lower boiling hydrocarbon products which are suitable as feedstocks to other
refinery

units for conversion into higher value transportation

fuels.

From a chemical reaction viewpoint, coking can be considered as a severe thermal

cracking

process in which one of the end products is carbon (i.e., coke). Actually the coke formed
contains

some volatile matter or high-boiling hydrocarbons. To eliminate essentially all volatile

matter from

petroleum coke it must be calcined at approximately 2000 to 2300°F (1095 to 1260°C).

Minor

amounts of hydrogen remain in the coke even after calcining, which gives rise to the
theory held

by some authors that the coke is actually a

polymer.
Coking was used primarily to pretreat vacuum residuals to prepare coker gas oil
streams suitable

for feed to a catalytic cracker. This reduced coke formation on the cracker catalyst and
thereby

allowed increased cracker throughputs. This also reduced the net refinery yield of
low-priced

residual fuel. Added benefit was obtained by reducing the metals content of the catalytic
cracker

feed
stocks.

In recent years coking has also been used to prepare hydrocracker feedstocks and to
produce a

high quality ‘‘needle coke’’ from stocks such as heavy catalytic gas oils and decanted
oils from

the fluid catalytic cracking unit [19,20]. Coal tar pitch is also processed in delayed
coking units

[16]. Delayed coking is described in Sections 5.2 to 5.7. This is the most widely used
coking

process. Fluid coking and Flexicoking are described in Sections 5.7 to 5.10. These fluid
bed

processes have been under development by Exxon over the past 40 years and are now

commercially operated in several refineries around the world

[17,20].

5.1 TYPES, PROPERTIES, AND USES OF PETROLEUM

COKE
There are several types of petroleum coke produced depending upon the process used,
operating

conditions, and feedstock properties. All cokes, as produced from the coker, are called
‘‘green’’

cokes and contain some high-molecular-weight hydrocarbons (have some hydrogen in

the

molecules) left from incomplete carbonization reactions. These incompletely carbonized

molecules are referred to as volatile materials in the coke (expressed on a moisture-free

basis).

Fuel grade cokes are sold as green coke, but coke used to make anodes for aluminum
production

or electrodes for steel production must be calcined at temperatures from 1800 to

2400°F (980 to

1315°C) to complete the carbonization reactions and reduce the volatiles to a very
low level.

Much of delayed coker coke is produced as hard, porous, irregular-shaped lumps

ranging in size

from 20 inches (50 cm) down to fine dust. This type of coke is called sponge coke
because it

looks like a black

sponge.

A second form of petroleum coke being produced in increasing quantities is needle

coke. Needle

coke derives its name from its microscopic elongated crystalline structure.
Needle coke is

produced from highly aromatic feedstocks (FCC cycle oils, etc.) when a coking unit is
operated

at high pressures [100 psig (690 kPa)] and high recycle ratios (1:1). Needle coke is
preferred

over sponge coke for use in electrode manufacture because of its lower electrical
resistivity and

lower coefficient of thermal

expansion.
Occasionally a third type of coke is produced unintentionally. This coke is called shot
coke

because of the clusters of shot-sized pellets which characterize it. Its production usually
occurs

during operational upsets or when processing very heavy residuals such as those from
some

Canadian, Californian, and Venezuelan crudes. These shot clusters can grow large
enough to plug

the coke drum outlet (12 in. or 30 cm). It is also produced from some high sulfur
residuals [13].

Shot coke is undesirable because it does not have the high surface area of sponge
coke nor the

useful properties, characteristic of needle coke, for electrode

manufacture

The main uses of petroleum coke are as

follows:

1. Fuel ​2. Manufacture of anodes for electrolytic cell

reduction of alumina

3. Direct use as chemical carbon source for manufacture of elemental phosphorus,

calcium

carbide, and silicon

carbide
4. Manufacture of electrodes for use in electric furnace production of elemental
phosphorus,

titanium dioxide, calcium carbide, and silicon

carbide

5. Manufacture of
graphite
Petroleum coke characteristics and end uses by source and type are given in Tables
5.1 and 5.2.

It is important to note that petroleum coke does not have sufficient strength to be used
in blast

furnaces for the production of pig iron nor is it generally acceptable for use as foundry
coke. Coal-

derived coke is used for these purposes. Typical analyses of petroleum cokes and
specifications

for anode and electrode grades are summarized in

Table 5.3.

The sulfur content of petroleum coke varies with the sulfur content of the coker
feedstock. It is

usually in the range of 0.3 to 1.5 wt%. It can sometimes, however, be as high as 8%.
The sulfur

content is not significantly reduced by

calcining.

5.2 PROCESS DESCRIPTION—DELAYED

COKING

This discussion relates to conventional delayed coking as shown in the flow diagram in
Figure

5.1. See also Photo 3, Appendix E. The delayed coking process was developed to
minimize

refinery yields of residual fuel oil by severe thermal cracking of stocks such as vacuum
residuals,

aromatic gas oils, and thermal tars. In early refineries, severe thermal cracking of such
stocks

resulted in unwanted deposition of coke in the heaters. By gradual evolution of the art it
was found
that heaters could be designed to raise residual stock temperatures above the coking
point without

significant coke formation in the heaters. This required high velocities (minimum
retention time)

in the heaters. Providing an insulated surge drum on the heater effluent allowed
sufficient time for

the coking to take place before subsequent processing, hence the term ‘‘delayed
coking.’’

Typically furnace outlet temperatures range from 900–930°F (482–500°C). The higher
the outlet

temperature, the greater the tendency to produce shot coke and the shorter the time
before the

furnace tubes have to be decoked. Usually furnace tubes have to be decoked every
three to five

month
s.

Hot fresh liquid feed is charged to the fractionator two to four trays above the bottom
vapor zone.

This accomplishes the

following:
1. The hot vapors from the coke drum are quenched by the cooler feed liquid thus
preventing any

significant amount of coke formation in the fractionator and simultaneously condensing

a portion

of the heavy ends which are

recycled.

2. Any remaining material lighter than the desired coke drum feed is stripped
(vaporized) from the

fresh liquid
feed.
3. The fresh feed liquid is further preheated making the process more energy
efficient.

Vapors from the top of the coke drum return to the base of the fractionator. These
vapors consist

of steam and the products of the thermal cracking reaction: gas, naphtha, and gas oils.
The vapors

flow up through the quench trays previously described. Above the fresh feed entry in the

fractionator there are usually two or three additional trays below the gas oil drawoff tray.
These

trays are refluxed with partially cooled gas oil in order to provide fine trim control of the
gas oil

end point and to minimize entrainment of any fresh feed liquid or recycle liquid into the
gas oil

produc
t.

The gas oil side draw is a conventional configuration employing a six- to eight-tray
stripper with

steam introduced under the bottom tray for vaporization of light ends to control the initial
boiling

point (IBP) of the gas

oil.

Steam and vaporized light ends are returned from the top of the gas oil stripper to the
fractionator

one or two trays above the draw tray. A pump-around reflux system is provided at the
draw tray

to recover heat at a high temperature level and minimize the low-temperature-level heat
removed

by the overhead condenser. This low-temperature-level heat cannot normally be

recovered by heat
exchange and is rejected to the atmosphere through a water cooling tower or
aerial coolers.

Eight to ten trays are generally used between the gas-oil draw and the naphtha draw or
column top.

If a naphtha side draw is employed, additional trays are required above the naphtha
draw tray.

Major design criteria for coking units are described in the literature
[12,18].