Refinery Processes

COKE PLANT

1 SUMMARY

Coking is one of the older refining processes, and one that is becoming more important to
petroleum refiners. As the quality of the world’s crude oil supply continues to decrease, “bottom
of the barrel” processing is becoming more attractive. The problem facing most refiners today is
how to squeeze the last drop of marketable fuel (most notably gasoline) out of a barrel of crude
oil. Coking is a method that refiners use to accomplish this goal. The refinery coke plant has
been called the garbage can of the refinery because residual oils that are difficult or impossible to
process in other refinery processes can probably be refined in the coke plant.

Contrary to what the name coke plant might imply, the purpose of the process is not to produce
coke. In fact, the primary goal of most coke plant engineers is to minimize the amount of coke
produced per barrel of feedstock. The purpose of a coke plant is to convert heavy residual oils
(tar, asphalt, etc.) into lighter, more valuable motor fuel blending stocks. Coke is an unfortunate
by-product of the process.

Refinery coking is controlled, severe, thermal cracking. It is a process in which the high-
molecular weight hydrocarbon molecules in residuum (bottoms from the vacuum flasher in the
crude unit) are cracked or broken up into smaller and more valuable hydrocarbons. Coking is
accomplished by subjecting the feed charge to an extreme temperature (approximately 950 °F)
that initiates the cracking process. The light hydrocarbons that are formed as a result of the
cracking process flash off and are separated in conventional fractionating equipment. The
material that is left behind after cracking is coke, which is almost pure carbon. In addition to
coke, which is of value in the metal industry and in the manufacture of electrodes, the products
of a coke plant include

• gas (refinery fuel and LPG)

• unstabilized (wild) gasoline

• light gas oil

• heavy gas oil.

2 DELAYED COKING

The lion’s share of the world’s coking capacity is represented by the delayed coking process.
Delayed coking can be thought of as a continuous batch reaction. The process makes use of
paired coke drums. One drum (the active drum) is used as a reaction vessel for the thermal
cracking of residual oils. This active drum will slowly fill with coke as the process proceeds.
While the active drum is being filled with coke, a second drum (the inactive drum) is in the
process of having coke removed from it. The coke drums are sized so that by the time the active
drum is filled with coke, the inactive drum is empty. The process flow is then switched to the
empty drum, which becomes the active drum. The full drum becomes the inactive drum and is
decoked. By switching the process flow back and forth between the two drums in this manner,
the coking operation can continue uninterrupted. Figure 1 shows the major components of a
modem delayed coking plant.

The two operating variables that have the greatest effect on the efficiency of a delayed coker are

• furnace outlet temperature

• coke drum operating pressure.

If the temperature of the oil leaving the direct-fired furnace is too low, the cracking reactions will
not proceed far enough. This will result in a high amount of volatile combustible matter (VCM)
in the coke and a reduced production of lighter hydrocarbons. Coke that has a high VCM
content because of its higher BTU value may not be as undesirable if it is being sold as a fuel
source; however, this is usually not the case with petroleum coke. The outlet temperature of the
direct-fired furnace should be in the range of 950 to 1000 °F.

The operating pressure inside the coke drum will determine how much of the cracked
hydrocarbon will be flashed to a vapor and removed from the drum through the overhead vapor
line. Any hydrocarbon that does not flash to a vapor will eventually be cracked to coke. A large
portion of the cleaning opportunities in a coke plant will be related to maintaining the proper
coke-drum operating pressure. Most of the delayed cokers in use today have a design operating
pressure on the coke drum of 25 psig. Some of the newer low-coke-yield processes have
operating pressures of 15 psig or lower.

2.1 Process Flow

The residuum feed is charged to the bottom of the fractionator tower where it is mixed with the
condensed tower bottoms (recycle oil). The feed and recycle oil are drawn from the bottom of
the fractionator and pumped through a direct-fired furnace where they are heated to the desired
cracking temperature. At this temperature, the cracking reaction is rapid. The high mass velocity
of the oil through the furnace prevents the lay-down of coke inside the furnace tubes.

After being heated in the direct-fired furnace, the oil is charged to the bottom of the active coke
drum. The cracked light hydrocarbons rise to the top of the drum where they are removed and
charged to the fractionator for separation. The heavier hydrocarbons are left behind, and the
retained heat causes them to crack to coke.

The fractionator tower in a coke plant is sometimes called a combination tower because it serves
two functions. The lower portion of the tower acts as a surge tank for the residuum feed and
recycle oil. The upper portion of the tower acts as a product fractionator and operates in much
the same manner as an atmospheric distillation tower in a crude unit. The hot (approximately
800 °F) vapors from the coke drum overhead are charged to the lower portion of the fractionator.
The vapors enter the fractionator above the liquid level of the tower bottoms. As the vapors rise
through the tower, they are contacted by a down flowing reflux stream and the heavier hydrocar-
bons are condensed. Gas and wild gasoline are removed from the tower as an overhead product.
Gas oils are removed as side-draw products, and the heavier hydrocarbons are mixed with the
residuum feed and recycled back to the coke drum.

Heat is removed from the fractionator by overhead reflux and by the “pump-around” part of the
heavy gas oil fraction. Pump around involves removing part of the heavy gas oil fraction from
the tower, cooling it and then reintroducing the cooled gas oil into the fractionator at a point
midway between the light gas oil and heavy gas oil trays. The heat recovered from the gas oil is
used for steam generation or as reboiler heat for other processes.
2.2 Decoking

During the coking process, the active coke drum slowly fills up with coke. Once the active drum
is full, the feed from the direct-fired furnace is switched to the inactive drum (which is empty),
and the full drum is isolated. The full drum is steam purged to remove any light hydrocarbons
that may be present in the coke, and then filled with water to cool the drum and coke.

After cooling, the covers are removed from the top and bottom of the coke drum and a pilot hole
is drilled through the center of the coke mass using high-pressure water. Once the pilot hole is
drilled, the coke is broken up by pumping high- pressure water through a rotating cutting tool
that is lowered through the pilot hole. The cut coke falls out of the bottom of the drum into rail
cars or trucks for shipment.

After the coke has been removed from the drum, the top and bottom covers are replaced and the
drum is steam purged to remove air. The drum is then heated to near operating temperature by
allowing some of the hot overhead vapors from the active drum to back up into the decoked
drum.

The decoking process (from cool-down to warm-up) will typically take from 17 to 22 hr. Most
coke drums are sized to be filled in 24 hr. This allows 2 to 7 hr. for slippage in the decoking
steps.

2.3 Process Metallurgy

The metallurgy of the process side of a coke plant is mainly stainless steel, with some carbon
steel. The feed to a coker has a high concentration of sulfur. These sulfur compounds will crack
at a high temperature to form H2S and other active sulfur compounds. Naphthenic acids may
also be present.

To a large extent, cokers are constructed of 410 stainless steel. This can be either as a liner over
carbon steel or as solid construction. Type 316 stainless steel might be used in cases where the
naphthenic acid concentration is high.

The metallurgy of the auxiliary (lube oil, seal oil, steam, etc.) systems in the coke plant will be
primarily carbon steel.
3 TYPES OF FOULING

Coke is the most common type of fouling that is found in a coke plant. These deposits can be
found in the direct-fired furnace tubes, transfer lines between the furnace and the coke drums,
vapor line between the coke drum and the fractionator and the bottom of the fractionator.
Chemical solvents are generally ineffective at dissolving coke deposits.

The fractionator and associated equipment (steam strippers, pump-around coolers, etc.) will
become fouled with a primarily organic deposit that can have a fairly high coke content. This
coke will have been carried over from the coke drum. An alkaline oxidizing stage can be used to
dissolve the organic binder that holds these deposits together. Emulsions of dilute caustic soda
in diesel fuel have also been used to clean coke plant fractionators. Fractionator deposits can
have high concentrations of sulfides, cyanides and arsenic. When these materials are dissolved
in acidic solvents, poisonous gases can be evolved. Steps must be taken (i.e., using the solvent
system or venting to a flare) to minimize personnel exposure to these hazards. As with most
product-side refinery deposits, laboratory testing of representative samples is the best guide in
the solvent selection process.

Since the products leaving the coke plant will have to be cooled and the temperatures are quite
high, significant water-side fouling of heat exchange equipment can be expected. These types of
fouling will consist of water hardness deposits and corrosion products, and are generally soluble
in acid-base and chelant-base solvents.
4 CLEANING OPPORTUNITIES

Fractionating equipment (tower, steam strippers, heat exchangers, etc.) will become fouled
during operation and require periodic cleaning. Fouled fractionating equipment not only
interferes with product separation, but it also causes an increased pressure in the coke drum. As
mentioned earlier, this can result in an undesirable increase in the coke yield.

Because of the high temperatures that are associated with coking, the water side of the cooling
system is subject to a high degree of fouling. As such there are many opportunities for cleaning.

There are a large number of auxiliary systems in a coke plant, including

• lube oil systems

• seal oil systems

• steam lines

• fuel lines

• air lines, etc.

These systems will require at least a preoperational cleaning and, in the case of process upsets,
possibly occasional operational cleanings.

Another service, offered by BJ Services is to provide backup decoking pumps to refineries.

Most coke plants have two high-pressure water pumps that they use to remove coke from the
coke drums. One pump is used for decoking, and the other is a backup in case of a mechanical
failure of the first pump. These pumps are a high maintenance item and require frequent repair.
Many refiners are very uncomfortable when one of these pumps is going to be down for any
length of time and they no longer have a backup pump. The coke plant is a bottleneck in residual
crude processing; therefore, if a coke plant has to shut down because it cannot cut coke, it can
also shut down significant portions of the rest of the refinery.

5 CLEANING TECHNIQUES
When chemical solvents are effective, the application techniques used will be no different from
those used in other process units. There are a number of methods that could be employed to
clean the towers found in coke plants. These include

• fill and circulate

• cascade circulation

• vapor degreasing (vapor phase).

Heat exchangers are probably best cleaned by fill-and- circulate chemical cleaning.

The method used to clean piping systems (steam lines, fuel lines, etc.) will be determined by the
type of material that is to be removed and the configuration of the piping system. Piping systems
that have parallel systems that can be used to form a circulation loop are good candidates for the
fill-and-circulate cleaning technique. The vapor-phase cleaning technique should be considered
for systems that require extensive temporary piping to form circulation loops.

Slug or surge flushing with water and air is applicable when cleaning piping systems, provided
that only particulate removal is to be accomplished and no chemical cleaning is required.

Consideration should be given to the use of emulsions and chelants as a solvent whenever
possible. For a number of years, waste minimization has been an increasing concern for BJ
Services customers. Waste volumes can be drastically reduced by using emulsions and chelants.
Emulsions are single-fill solvent systems that permit the simultaneous removal of many mixed
organic/inorganic deposits. The use of chelants will often permit inorganic scale dissolution,
neutralization and passivation with a single-fill solvent.

Hydroblasting is by far the greatest service that is utilized in a coke plant. Most of the product-
side deposits that are found in a coke plant are pure coke or contain large amounts of coke, and
are difficult or impossible to remove by chemical cleaning.