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.

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.

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 980 to 1315°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 feedstocks.

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. Coal tar pitch is also processed
in delayed coking units.

Types, Properties, and Uses of Petroleum Coke:

Table 1: Petroleum Coke Characteristics

Process Coke type Characteristics
Delayed; 1. Sponge; Sponge like appearance.
Higher surface area.
Lower contaminates level.
Higher volatile content.
Higher HGIa (~100).
Typical size of 0–6 in. (0–15 cm).
2. Shot; Spherical appearance.
Lower surface area.
Lower volatiles.
Lower HGIa (< 50).
Tends to agglomerate.
3. Needle; Needle like appearance.
Low volatiles.
High carbon content.

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 Fluid; Fluid; Low volatiles
Higher contaminates level.
Low HGIa (< 40).
Black sand-like particles.
Flexicoker; Flexicoke; Highest metals level.
80% < 200 mesh.
a = Hardgrove grindability index.

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 a chemical carbon source for manufacture of elemental phosphorus, calcium carbide, and silicon
carbide.
4. Manufacture of electrodes for use in electric furnace production of steel, elemental phosphorus, titanium
dioxide, calcium carbide, and silicon carbide.
5. Manufacture of graphite.

Process Description — Delayed Coking:

This discussion relates to delayed coking as shown in the flow diagram in Figure 1.

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.

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Hot fresh liquid feed is charged either directly to the furnace or to the fractionator two to four trays above the bottom
vapor zone. If the feed is charged directly to the furnace, it is frequently referred to as a zero recycle operation even
though a small amount of recycle is added to the fresh feed.

Charging to the fractionating column 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 draw-off 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
product.

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.

Coke Removal:

When the coke drum in service is filled to a safe margin from the top, the heater effluent is switched to the empty coke
drum and the full drum is isolated, steamed to remove hydrocarbon vapors, cooled by filling with water, and drained;
the top and bottom headers are removed; and the coke is cut from the drum.

The ecoking operation is accomplished in some plants by a mechanical drill or reamer; however, most plants use
a hydraulic system. The hydraulic system is simply a number of high-pressure [2,000 to 4,500 psig (13,800 to 31,000
kPa)] water jets that are lowered into the coke bed on a rotating drill stem. A small hole [18 to 24 in. (45 to 60 cm) in
diameter] called a rat hole is first cut all the way through the bed from top to bottom using a special jet. This is done to
allow the main drill stem to enter and permit movement of coke and water through the bed.

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The main bulk of coke is then cut from the drum, usually beginning at the bottom. Some operators prefer to begin at the
top of the drum to avoid the chance of dropping large pieces of coke, which can trap the drill stem or cause problems in
subsequent coke-handling facilities. Today, some operators use a technique referred to as “chipping” the coke out of the
drum. In this technique, the cutting bit is repeatedly transferred back and forth from top to bottom as the hydraulic bit
rotates, and the coke is cut from the center to the wall. This reduces cutting time, produces fewer fines, and eliminates
the problem of the bit being trapped.

The coke that falls from the drum can be collected directly in railroad cars. Alternatively, it, along with the cutting
water, is dumped from the bottom of the coke drum onto a concrete pad or into a sump, where the water is drained off
and recycled to be used for the cutting operation. The coke is transferred by conveyor belt to storage or to a calciner.
Sometimes, it is sluiced or pumped as a water slurry to a stockpile or conveyed by belt.

Calculation Method:

- The naphtha or gasoline fraction may be split into light and heavy cuts. After hydrotreating for sulfur removal
and olefin saturation, the light cut is either isomerized to improve octane or blended directly into finished
gasoline.
The heavy cut is hydrotreated and reformed. A typical split of coker naphtha is as follows:

Light naphtha=35.1 vol . % , ° API=65

Heavy naphtha=64.9 vol . % , ° API=50

- The gas oil fraction is usually split into a light and a heavy cut before further processing. The light fraction
may be used as hydrocracker feed or hydrotreated and subsequently fed to an FCC.
The heavy fraction may be used as heavy fuel oil or as FCC feed after hydrotreating, or sent to the vacuum
distillation unit. An approximate split of the coker gas oil can be estimated from the following:

Light gas oil(LCGO)=67.3 vol .% ,° API=30

Heavy gas oil(LCGO)=32.7 vol. % ,° API ≈13

The yield data have been developed from correlations of actual plant operating data and pilot
plant data. Values calculated from these equations are sufficiently accurate for primary
economic evaluation studies (Table 2 for calculating yields when the Conradson carbon value is
known); however, for the actual design of a specific coking unit, the yields should be
determined by the pilot plant operation.

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 Table 2: Coke Yields when Conradson Carbon Is Known.
a
Coke wt . %=1.6 ×(wt . % Conradson carbon )
Gas ¿
a
Gasoline wt . %=11.29+ 0.343( wt .% Conradson carbon )
Gas oil wt . %=100−wt . % coke−wt . % gas−wt . % gasoline
186.5 b
Gasoline vol . %= ×(gasoline wt . %)
(131.5+° API )
155.5 b
Gas oil vol. %= ×(gas ollwt . %)
(131.5+° API )

a = Use actual Conradson carbon when available.

b = All °API are those for net fresh feed to coker.

Note: These yield correlations are based on the following conditions:

1. Coke drum pressure 35 to 45 psig.
2. Feed is “straight-run” residual.
3. Gas oil end point 875 to 925°F.
4. Gasoline end point 400°F.

Table 3: Coke Yields, East Texas Crude Residuals

Coke wt . %=45.76−1.78 ° API
Gas ¿
Naphtha wt . %=20.5−0.36 ° API
Gas oil wt . %=21.82+2.30 ° API
186.5
Naphtha vol . %= (gasoline wt .% )
(131.5+° API )
155.5
Naphtha vol . %= (gas oil wt . %)
(131.5+° API )

Table 4: Coke Yields, Wilmington Crude Residuals

Coke wt . %=39.68−1.60 ° API
Gas ¿
Naphtha wt . %=20.5−0.36 ° API
Gas oil wt . %=28.55+ 2.10° API
186.5
Naphtha vol . %= (gasoline wt .% )
(131.5+° API )
155.5
Naphtha vol . %= (gas oil wt . %)
(131.5+° API )

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In all cases, the weight and volume percentages given are based on the net fresh feed to the
coking unit and are limited to feedstocks having gravities of less than 18°API. The yields shown
will vary significantly if the coker feed is derived from material other than straight-run crude
residuals. The numerical values in the equations do not represent a high degree of accuracy
but are included for the purpose of establishing a complete weight balance.

Typical gas compositions and sulfur and nitrogen distributions in products produced by delayed
coking of reduced crudes are given in Table 2 and Table 3.

Table 5: Typical Gas Composition for Delayed Coking.

(Sulfur–Free Basis)
Component Mol.%
Methane 51.4
Ethylene 1.5
Ethane 15.9
Propylene 3.1
Propane 8.2
Butylene 2.4
i-Butane 1.0
n-Butane 2.6
H2 13.7
CO2 0.2
Total 100
Note: MWgas = 22.12

Table 6: Sulfur and Nitrogen Distribution for Delayed Coking

(Basis: Sulfur and Nitrogen in Feed to Coker)
Cut Sulfur (%) Nitrogen (%)
Gas 30 -
Light naphtha 1.7 -
Heavy naphtha 3.3 1
LCGO 15.4 2
HCGO 19.6 22
Coke 30 75
Total 100 100