Refining-Petrochemicals-Chemicals-Engineering

PDVSA
Venezuela
MSc in refining, engineering and gas
Course 2
Module 7: Refining processes (4)
HEAVY CUTS CONVERSION

3 - COKING PROCESSES

I - INTRODUCTION.............................................................................................................................1
II - GENERAL DESCRIPTION OF THE COKING PROCESSES ......................................................1
III - DELAYED COKING PROCESS.....................................................................................................3
1
2
3
4

Process description .......................................................................................................................... 3

Process performances...................................................................................................................... 4
Uses and further refining or products .............................................................................................. 4
Conclusion......................................................................................................................................... 5

IV - FLUID COKING PROCESS............................................................................................................6

V - FLEXI COKING PROCESS............................................................................................................7
VI - LIQUID PRODUCTS HYDROTREATING......................................................................................9
1 2 3 -

Naphtha hydrotreating ...................................................................................................................... 9

Jet fuel and diesel fuel hydrotreating............................................................................................... 9
Heavy Gasoil hydrotreating.............................................................................................................. 9

VII - COKE GAS DESULFURISATION................................................................................................10

VIII - HYDROGEN MANAGEMENT......................................................................................................11
IX - CONCLUSION ..............................................................................................................................11

RA COK - 02055_A_A - Rev. 2

25/03/2008

2008 ENSPM Formation Industrie - IFP Training

I-

INTRODUCTION
The coking process is used for the deep conversion of residues into light fractions with the total destruction
of the heavy fuel oil and its replacement by a solid fuel as byproduct. The objectives of this conversion
process are:
-

to upgrade heavy, high sulfur low quality bottom (high sulfur fuel oil blendstock) by
converting it to lighter products which can ultimately be converted to clean gases, gasoline
and distillate. In addition, the process frees substantial amounts of premium distillate flux
stock which previously had been used for fuel oil blending.

to enable desulfurisation of a high sulfur, high metals vacuum residuum; producing a low to
ultra low sulfur fuel oil product plus naphtha and distillate.

to upgrade heavy, high viscosity crudes in the production field to synthetic crudes which can
easily be handled in a refinery.

to concentrate substantially feedstock sulfur, nitrogen, Con Carbon and metals in the
residual coke.

Coking is in fact the final step in thermal cracking of petroleum residues. Recent developments in the coking
process have been aimed at reducing the solid fuel produced. The existing coking processes include:
Delayed coking
Fluid coking
Flexicoking
These three versions of the process are based on the same reactions and are designed to meet the same
refining objectives.
Coking products require further treatment if they are to be used in the conventional refinery product pool.
This factor has to be taken into account when coking is compared to other residue conversion processes.

II -

GENERAL DESCRIPTION OF THE COKING PROCESSES

All these processes are implemented in a relative low pressure range (0.05 to 2 MPa) and in a relatively high
temperature range (430 to 850C).
The liquid and gaseous fractions issued from the cracking of heavy fractions are rich in aromatic
hydrocarbons and especially in olefins.
All these processes are endothermic. The transformations involved proceed by thermal activation and take
place according to a free-radical mechanism.

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2008 ENSPM Formation Industrie - IFP Training

Description of reactions mechanism

Asphaltenes and resins can effectively give rise, well before 400C, to free radicals which in turn intervene in
various ways as it is diagrammed in Table 1. These radicals, having very complex molecular structure, can do
the following:
-

(1) initiate their own cracking

(2) activate the molecules of the surrounding substrate

(3) react between themselves to give rise to new asphaltenes having higher molecular
weight, which in turn may be activated and condensed, and this free-radical condensation
ends up as coke

(4) capture radicals issuing from the initiation or cracking of lighter molecules from the
surrounding substrate and slow down the transformation of this substrate

(5) be fixed by hydrogen issued from a molecule having a hydrogen donor power (naphtheno
aromatic molecules).

Likewise, asphaltenes and resins can also play the role of donor solvent, either directly via hydrogen from
naphthene rings coupled with their aromatic pericondensed rings, or indirectly via hydrogen sulfide and
mercaptans issued from the cracking of the C-S bonds included in lateral chains of aromatic nuclei and
heterocycles. This role of donor solvent also participates in slowing down the cracking of light molecules by
the capture of radicals that initiate or propagate secondary cracking. On the other hand, this hydrogen transfer
from asphaltenes and resins to other molecules or radicals can only speed up their condensation and
demixing.
During all these transformations, there is some selectivity in the breaking of the different chemical bonds. Only
the most unstable ones are broken, i.e. those of which the bonding energy is weaker, as shown in table 1. The
majority of the sulfur atoms and all the nitrogen atoms of the heterocyclic type belonging to the resins and
asphalthenes are rejected in the coke.

02055_A_A

2008 ENSPM Formation Industrie - IFP Training

General performances:

Coking is a non catalytic thermal cracking process based upon the concept of carbon rejection. The
heaviest, hydrogen deficient portions of the feed (i.e., asphaltenes and resins) are rejected as coke which
contains essentially all the feed metals, ash and a substantial portion of the feed sulfur and nitrogen :
Feed sulfur removal from liquid products ranges from 40 to 75% in the coker, depending
on the feed Conradson Carbon
Feed nitrogen removal from liquid products is greater than 50% in the coker

Because coking is a thermal process, it can process any feedstock quality. It can handle virtually any
pumpable hydrocarbon (e.g. vacuum resid, atmospheric resid, tar sand bitumen, heavy whole crudes,
shale oil, catalytic plant bottoms).

Representative yield data of vacuum residue coking are:

10-13 wt% gas product
60-70 LV% total liquid product
20-35 wt% raw petroleum coke

III -

DELAYED COKING PROCESS

Delayed coking is a semi-continuous process for upgrading residual stocks to naphtha, gas oil, coke (most of
the time this is a by-product), and by-products gas.
For coke production, mainly for high grade coke, delayed coking can be applied on rich aromatic distillates or
on particular selected residues.
Delayed cocking technology can be obtained from several contractors, including Lummus, Braun, FosterWheeler and Conoco on a non-proprietary basis.

1-

PROCESS DESCRIPTION
In the delayed coking process (see Figure 1) the heavy residue is pumped to the bottom of the
combination tower which acts as an accumulator for the feed to the coking furnace as well as a
product fractionator.
The bottoms of the combination tower are pumped to the coking furnace where thermal cracking
takes place at 480-500C. Short residence times and high mass velocity (enhanced by steam injection
near the furnace entrance) are required to minimise coke deposition in the furnace tubes.
The furnace outlet stream goes to an upflow coke drum where the endothermic cracking reaction is
completed. Coke is deposited in the drum (20 to 37 m high, 6 to 9.1 m diameter) at 425-450C and
4-8 bars (only in high grade coke products. Normally for fuel grade coke, the pressure is 1 to 2 bars
(see Fig. 1)) while the vapors are sent to the combination tower for separation into various product
streams and recycle.
The upper portion of the combination tower serves to separate the cracked products from the coker.
Vapor from the top of the combination tower is condensed with a portion of the liquid naphtha returned
to the tower as reflux while the uncondensed vapor is sent to light ends.
The delayed coking process uses two coke drums which operate on sequenced 24 to 48 hour cycles
so that one drum is in its coking cycle while the other drum is being decoked. When one coke drum is
filled with coke, it is switched to a cooling and decoking cycle and an alternate drum is placed in
coking service.

02055_A_A

2008 ENSPM Formation Industrie - IFP Training

2-

PROCESS PERFORMANCES
The performances of the DELAYED COKER depend on:

operating parameters (pressure, temperature, recycle ratio)

characteristics of the feed (CCR Carbon Conradson, etc.)

Pressure

Liquid yield

Temperature

"

"

"

"

"

"

Recycle ratio

"

"

"

"

"

"

CCR

"

"

"

"

"

"

Coke yield

Gas yield

In fuel grade coker producers Operating Pressure is low to increase liquid yields. In anode grade
coker producers Operating Pressure is high due to coke characteristics requirement.
An example of DELAYED coking application to ARABIAN HEAVY vacuum residue is shown (table 2
and 3) in comparison with flexicoker performances.
Roughly, the coke yield is 1,5 time higher than the Conradson carbon level for typical operating
conditions.
The products characteristics (table 3) demonstrate a high olefinic character and a high concentration
of sulfur and nitrogen atoms.

3-

USES AND FURTHER REFINING OF PRODUCTS

Downstream treatment of coker products are dependent on needs of the refiner:

02055_A_A

essentially complete removal of sulfur can be achieved in C4-gas. This material can then be
used for refinery fuel, LPG recovery, or H2 manufacture. C 3/C4 can be used as alkylation
plant feed.

more than 90% desulfurisation can be achieved on coker naphtha via conventional
hydrotreating. Hydrotreated naphtha is suitable for refinery fuel, mogas blending, or sold as
a petrochemical feedstock.

coker gas oils can be further converted to more valuable naphtha via cat cracking or
hydrocracking.

2008 ENSPM Formation Industrie - IFP Training

Coke types and uses

The type of coke produced, either electrode, metallurgical or fuel grade, has a significant effect on the
overall economics of the delayed coking.
Coke produced in delayed coking (green coke) contains volatile combustible material (VCM) and
moisture. Calcining is the treatment step where the moisture and VCM are reduced and the fixed
carbon is raised to over 90 wt%. Graphitization is the process which converts calcined coke into
finished electrodes.
Many different types of coke can be produced depending on the feed characteristics and operating
conditions. Impurities in the feed to the coker, sulfur, nickel, vanadium, etc., will be concentrated in the
coke. The structure of the delayed coke will be affected by the naphthenic/aromatic content of the feed
to the coker.
Needle coke has large interconnected pores surrounded by thick walls. Aromatic feedstocks with
most of their components boiling above 425C have high potential for producing needle coke.
Honeycomb coke has uniformly distributed elliptical pores.
Sponge coke has small, non connected pores surrounded by very thick walls; it is the usual form of
delayed coke.
Fuel grade coke: high in sulfur and metals (shot coke type) and typical in high CCR crudes. This is
produced by most American cokers as refineries are only interested in high liquid yields, not coke,
and to increase profit by processing heavy and low cost crudes.
The markets for coke depend on coke quality. The use of high sulfur and metal rich coke is limited to
fuel applications: utility and power plants, cement kilns. The higher quality cokes are used as:

4-

calcined coke for production of amorphous carbon anodes after graphitization used in the
manufacture of primary aluminium; sulfur is limited to 3% max and vanadium to 200 ppm
max

metallurgical coke for blending with high quality coking coals; sulfur limit is a function of
coal quality; metal content is not a limiting specification.

CONCLUSION
This process has been in existence for quite a long time. It is widely used in the United States to
reduce heavy fuel oil production and to increase motor fuels. The gas oil and distillates produced by
the unit can be converted into gasoline in additional catalytic conversion units such as the FCC unit.
However few units of this type exist in European refineries.

02055_A_A

2008 ENSPM Formation Industrie - IFP Training

IV - FLUID COKING PROCESS

Fluid coking was developed by Exxonmobil and first commercialised about 50 years ago. Fluid coking units
are in operation at 8 locations in units ranging in size up to 72,000 bbl/d as shown in Table 1. Total feed
capacity of about 8400 ton/d. About one-half of this feed capacity is accounted for by two units operated by
Syncrude Canada, in Alberta, to process bitumen extracted from the Athabasca tar sands.
Process Description
The fluid coking process is a fluidised-bed process. The circulating fluid bed medium is the coke that is
deposited from the feedstock. The feed is sprayed into a fluidised bed of hot coke particles in a reactor vessel
at a temperature of 480-540C where its cracks to produce lighter liquids and gases and more coke. The coke
is circulated to the burner vessel where a portion of the coke is burned with air in a fluidised bed, increasing
the temperature to well above of that of the reactor vessel. Heated coke is recirculated back to the reactor
vessel to supply the heat of reaction. See the scheme shown in Figure 3.
The reaction temperature is higher than in delayed coking, and the gross coke yield is 75-80% of that
produced by delayed coking. A portion of the coke, about 6% wt of feed, is burned in the process to supply the
heat of reaction, and the reminder is withdrawn continuously. Therefore, the net coke yield will be 60-65% of
that produced by delayed coking, or equal to the carbon residue content of the feed.
The coke is a finely divided powder and is very low in volatile matter. It may be further pulverised and burned
together with a more volatile support fuel in specially designed furnaces.
The vaporised products from the reactor are first scrubbed to remove coke dust and heavy ends, which are
recycled to control the end point of the distillate, and then are fed to a fractionator and separated into a gas
stream, a naphtha and a heavy gasoil. Because the high temperature employed in the reactor, the gasoil end
point is high (525-565C). The distillate fractions are also quite olefinic and aromatic and normally require
extensive hydrotreating.
Process Performances
The flue gas contains about 4% combustibles, 42% steam and 54% inerts and has a heating value of about
20 Btu/scf., and coke dust, and must normally be incinerated in a CO boiler and subsequently treated to
remove particles and sulphur oxides.
As with delayed coker, there are no limitations on feedstock quality. The process can handle virtually any
pumpable feedstock.
Fluid coking produce higher liquid yields and less coke than delayed coking. Furthermore it is a continuous
process.
As the delayed coking process, a major disadvantage of FLUID COKER is the production of large quantities of
coke product; it is subject to similar quality marketing constraints.
Outlets for coke include:

steel industry if sulfur low

fuel in steam/power plants and cement kilns

Normal outlet for coke is combustion in coke-fired steam boiler. it requires:

specially designed grass-roots boilers

no severe environmental restrictions regarding sulfur emissions.

No fluid cokers have started up since 1978 because of the high costs of the flue gas scrubbing and the low
value of the very hard and low volatile content coke. There is now renewed interest in fluid coking, in part
because the coke is now being used in circulating fluidised beds boilers for power generation and for other
uses such as cement kiln fuel. More importantly, evolutionary improvements by operators have improved
yields, extended run lengths and reduced overall costs.
02055_A_A

2008 ENSPM Formation Industrie - IFP Training

Eight units with a combined capacity of 375,000 bbl/d were built between about 1954 and 1978. A new unit
vacuum residue capacity of 95,000 bbl/d is under construction for Syncrude Canada in Alberta's Athabasca oil
sands region.

V-

FLEXI COKING PROCESS

Flexi coking was developed by Exxonmobil as an extension of its fluid coking technology and commecialised
in 1976. The basic idea was to convert coke to a useful, sulfur free gas as an integral part of the process. Five
units have been build worldwide with a total feed capacity of 179,000 bbl/d and 963 t/d of coke as shown in
Table 5.
Process Description
A simplified flow scheme of the Flexi coking process is shown in Figure 4. The process includes three fluidised
vessels: the reactor, the heater and the gasifier.
The reactor is identical to that used in a fluid coker; the heater vessel has replaced the burner vessel but
serves the function of supplying the heat to the reactor; the gasifier has been added to gasify the net coke
with air and steam to produce a low heating value (100-120 Btu/scf, 890-1060 kcal/Nm3) fuel gas. Plants are
designed for withdrawal of only a small amount of coke, amounting to 0.5-2% of the feed, to remove metal
contaminants in the feed, which builds up in the coke. Coke is circulated from vessel to vessel. The gasifier is
the highest temperature vessel, operating at about 980C. Coke and gas from the gasifier are used to bring
the coke in the heater vessel to an intermediate temperature; coke from the heater is circulated to the reactor
to provide the heat of reaction for the process.
The yields and properties of the hydrocarbon products from the reactor are identical to those from a fluid
coker.
The fuel gas from the gasifier as the following typical composition after H2S removal:
Composition
CO

17.4

H2

17.8

C1-C4

1.4

CO2

10.0

N2

48.7

H 2O

HHV, Btu/scf

4.7
____
100
127

Kcal/m3

1130

Available pressure
Bar

02055_A_A

% vol

Psig

10
0.7

2008 ENSPM Formation Industrie - IFP Training

The total thermal value of the gas will be 90-95% of the thermal value of the net coke that is gasified.
The gas is passed through a cyclone and then scrubbed to remove coke fines. The dust is extremely fine and
requires special handling for disposal.
The gas as produced contains essentially all of the sulfur present in the coke. About 98% of the sulfur is
present as H2S and 2% as COS. This gas is scrubbed by one of Exxon's Flexisorb solvent to reduce H2S and
COS contents to about 100 ppm each.
The treated gas contains about 20% each of H2 and CO. The low-Btu gas has been used in refinery process
heaters and in steam generating and superheating boilers.
The advantage of this process is the fact that it almost totally eliminates coke production. However this
assumes there are local outlets for the gas produced, despite of its low heating value and its too low pressure
for long distance transportation.
A variation of this process uses pure oxygen instead of air for gasifying coke. This produces a mixture of
carbon monoxide and hydrogen (CO + H2) which can be used as synthesis gas.
The performances obtained by FLEXICOKING on SAFANIYA vacuum residue are shown above in tables 2
and 3 compared to DELAYED COKING.
No fundamental differences can be observed between the products qualities. The products have also to be
hydrotreated.
Coke that is purged in the process is highly concentrated in metals. Some of this coke is sold for metal
(vanadium - nickel) recuperation. Not all the coke can be gasified as metal will start to accumulate in the
gasifier.
Process Performances
Exxon continues to look for ways to improve operability and to increase run length. Typical run length are 1824 months. The longest flexicoker run has been 36 months at the Shell refinery in Martinez, California.
In conventional operation, the 525C+ bottoms is recycled from the scrubber to the reactor. In once-through
operation, the feed is injected directly into the reactor, and the bottoms is removed as another product.
Comparative yields and stream properties for recycle and once through processing are shown in Table 4. The
bottoms is a low-liquid product containing about 20% CCR and some entrained coke fines, which may be
removed with hydrocyclones and recycled to the reactor. An alternative disposition is to recycle the bottoms
back to the vacuum flasher to recover the 565C end point gasoil with the vacuum gasoil.

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2008 ENSPM Formation Industrie - IFP Training

VI - LIQUID PRODUCTS HYDROTREATING

The coking process provides the conversion of heavy bottoms to lighter distillates, but the liquid products must
be further refined to meet the stringent product specifications. The coker products are higher in olefin,
aromatic, nitrogen and sulfur contents than either virgin or catalytically processed oils. By using hydrotreating
process, impurities such as sulfur and nitrogen can be eliminated, and olefins can be satured to the more
stable paraffinic and naphthenic structures. Multiple aromatic rings can be saturated to lesser ring structures
and to naphthenes as required for downstream catalytic cracking feeds or for blending to diesel oil and jet fuel
product specs.

1-

NAPHTHA HYDROTREATING
The processing objective is to produce a naphtha that is suitable to be processed in todays modern
bimetallic catalytic reformers (usually < 1.0 vol percent olefins and < 1.0 wppm of nitrogen and sulfur).
A C5-170C coker naphtha cut is processed. LPG treatment can also be done in this unit, if needed.
The feedstock, the products and problems encountered in such treatment are shown in table 6 above
(fluid coker products).

2-

JET FUEL AND DIESEL FUEL HYDROTREATING

The diesel/jet fuel hydrotreating unit can process either a 180-280C cut for jet fuel production or a
180-350C cut for diesel fuel. Of the three hydrotreating processes, the diesel/jet hydrofining unit has
probably the most challenging job to perform when working on 100 percent coker distillate. Besides
reducing sulfur and nitrogen, this unit must also saturate aromatics to produce the required diesel
cetane index and the required jet fuel smoke point. The proper selection of catalyst and operating
conditions is required to reach the product quality goals. This unit is characterised by relatively high
pressures and high hydrogen intake and must be properly designed to control the exothermic olefin
and aromatic hydrogenation reactions.
An example of such hydrotreating is shown in table 6 on fluid coker products. The objectives of
hydrotreating these unsatured gasoils can be different :

a simple stabilisation can be performed by low severity hydrogenation

a deep cetane improvement will require high severity hydrogenation.

The operating conditions will be very different. Such examples are shown in table 7.

3-

HEAVY GASOIL HYDROTREATING

Heavy coker gasoil corresponds to a straight run vacuum gasoil fraction (350-510C).
The hydrotreating unit processes 100 percent heavy coker gasoil (375-530C) to a satisfactory cat
cracker feedstock.
The unit produces a substantial quantity of middle distillate product and some naphtha as a result of
the extreme processing of the heavy coker gasoil (81-87 percent HDN and 99 percent HDS). An
example of such treatment is shown in table 7.

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2008 ENSPM Formation Industrie - IFP Training

10

This conversion of the feed to lighter products is primarily due to a boiling point reduction
associated with sulfur and nitrogen removal and hydrogenation of multi-ring aromatics. Some direct
carbon-carbon bond breakage also occurs. While the additional distillate and naphtha produced brings
a conversion credit to the refiner, their quality might need to be improved if their outlet is into the
automotive products market.
The distillate product, which is extremely low in sulfur and nitrogen relative to heating oil specs, is high
in aromatics. This product would, therefore, not meet the potentiel future specifications on jet and
diesel fuels. Further hydrogenation of this material within the hydrotreating unit would not be
economical and would be best carried out in a separate unit. This additional processing would not be
required if the disposition of this material were the heating oil market.
The C5-180C naphtha fraction produced in the hydrotreating unit is fairly high in organic nitrogen
content, approximately 20 wppm. This material by itself would, therefore, not be a suitable feedstock
to an existing virgin naphtha pretreater upstream of a catalytic reformer. It can be easily upgraded in
the coker naphtha hydrofining unit. Alternatively, the naphtha could be treated in the Diesel/Jet
hydrofining unit or possibly just blended with the virgin naphtha depending on the final naphtha pool
properties.

VII - COKE GAS DESULFURIZATION

The flexicoking process does not produce coke but produces a lot of gas to be treated before uses.
Background
The coke gas leaving the heater contains sulfur mainly in the form of H2S and some COS. The sulfur
content of the gasified coke is a function of the feed sulfur.
Scrubbing processes are available which remove essentially the whole H2S but do not remove the
COS.
Process selection
The choice of H2S removal process should be based on economic study considering degree of
desulfurisation required to meet overall refinery sulfur emission targets.
In modern units, an amine scrubbing system, using a specially developed amine called Flexisorb, is
employed. Flexisorb scrubbing allows a very high H2S removal efficiency and is highly selective for
H2S over COS.
Downstream Claus plant and tailgas cleanup facilities are required to dispose of the H2S rich stream
coming from the Flexisorb regenerator.

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2008 ENSPM Formation Industrie - IFP Training

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VIII - HYDROGEN MANAGEMENT

Since the coker products are deficient in quality relative to virgin cuts, additional hydrogen is needed to
hydrotreat them to the very stringent product qualities (Table 6).
A big advantage of the COKING/Hydrotreating route is that no hydrogen is added to the highly contaminated
bottom of the barrel. The heavy material boiling above the recycle cut point (nominally 510C) is recycled to
extinction in the reactor, and the associated sulfur, nitrogen and metals are rejected to coke.
Hydrogen requirements for all of the hydrotreated coker products are near 150 l/l of coker feed on (Arab
Heavy). This hydrogen could be manufactured using some of the light ends produced in the coking unit or
refinery fuel or natural gas.

IX - CONCLUSION
COKING process initially seems to be a very attractive process for heavy feedstock conversion, particularly
for vacuum residues of conventional or extra heavy crudes because no major limitations appear in their uses
(metals, sediments ).
The investment remains limited (low pressure equipment) for delayed coker.
But, several problems have to be pointed out:

the high grade cokes cannot be produced from heavy feedstocks because low sulfur, low
metal and low nitrogen contents are required in that type of coke.

the production of coke in large quantities requires a market for such a product where all
contaminants are concentrated. The gasification of the coke by flexicoking considerably
complicates the overall system and increases the investment cost. In addition, generally
there is little outlet for the low BTU gas as a fuel

the converted products require further hydrotreatment to achieve sulfur, nitrogen and
aromatics reduction to reach product specifications. This operation is costly in investment
(hydrotreater at high severity) and in hydrogen consumption (same problem as for direct
hydrotreater)

the C1-C4 gas production is not attractive for refiners because this production limits the
overall liquid yield.

Processing heavy low cost crudes to increase profit have keeps the cokers running in the US and Venezuela.
In the future, COKING process may be used for extra heavy crude upgrading where other technologies are
limited, but the new trends in environmental problems and future product specifications are not
favorable to such processes.

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12

Table 1
POSSIBLE REACTION MECHANISM BONDING ENERGIES (kcal/mole)

Free radicals
HEAT
INITATION

A
R
As

PROPAGATION

A
R
As

DEALKYLATION

S + S1

A
R
As
S + AH
As +AH
R + R'H

C - C 82.6
C = C 145.8
C C 199.6

A
R
As

A1
R1
As1

S +

CRAKING

S +S1

ALKANES

S=2 + S3

CONDENSATION

A-R. As-As
As-R

H2 DONOR

SH + A
AsH + A
RH + R'

SOLVENT
C - H 98.7
H = H 104.2
C - O 85.5

C-S
-S - S
-S - H

65
84
83

C - N 72.8
C = N 147
C N 212.6

S : Satured
A : Aromatics
R : Resins
As : Asphaltens

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2008 ENSPM Formation Industrie - IFP Training

D CH 1075 A

S
A
R
As

13

Table 2
COKING PROCESSES COMPARISON: FEEDSTOCK AND MATERIAL BALANCE

FLEXI
COKING

DELAYED COKING
Feedstock

MEREY*

SAFANIYA V.R.

MESA*

SAFANIYA
V.R.

Specific gravity
Sulfur
Nitrogen
Conradson Carbon
Metals

1.07
4.06
7176
29.5
105.8

1.040
5.3
4600
24.2
255

1,017
1.83
6603
22.6
237

1.052
6.0
4800
27.7
269

8.31
7.09
18.78
25.62
40.18

2.1
11.1
13.5
17.9
17.1
38.3

11.99
17.70
18.15
20.25
32.19

1.5
12.3
10.8
18.0
26.4
0.7

Material balance wt%

H 2S
C1-C4
Naphtha
Light gasoil
Heavy Gasoil
Coke solid
Gasified

(32.5)

* Extra heavy Venezuelan crudes

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2008 ENSPM Formation Industrie - IFP Training

14

Table 3
COKING PROCESSES COMPARISON: PRODUCTS CHARACTERISTICS

FLEXI
COKING

DELAYED COKING
NAPHTHA

MEREY
(C5 - 330F)

Specific gravity
API
S (wt%)
N (ppm)
Bromine Number (mg/100 g)
LIGHT GASOIL

0.747
58
0.81
200
53.6

MESA
(C5 - 400F)
0.756
55.6
1.1
62
90

(330 - 680F)

Specific gravity
API
S (wt%)
N (ppm)
Bromine Number (mg/100 g)
Diesel Index

0.864
32.1
2.15
1400
40
43.1

HEAVY GASOIL

(680F+)

Specific gravity
API
S (wt%)
N (ppm)
Conradson carbon (wt%)
Metals (ppm)

0.978
13.2
2.95
6400

0.79
47.8
0.18
236
71
(400 - 680F)

0.875
30.2
3.9
800
45
36

0.79
47.6
0.33
1251
34.5
31.6

02055_A_A

(% wt)
(ppm)
(ppm)
(% wt)
(% wt)

0.879
29.5
3.4
950
NA
NA

(680F+)
0.978
13.2
5.3
4100
NA
4

0.980
12.9
0.98
2810

COKE
VCM
Ni
V
N2
S

0.747
58.0
1.1
70
122

12.5
464
2040
1.98
4.61

2008 ENSPM Formation Industrie - IFP Training

13.33
134
603
1.78
2.15

0.999
10.1
5.8
4600
4.8
1.7

15

Table 4
PRODUCT PROPERTIES
Recycle and Once-Thru Fluid Coking Yields and Product Properties
Feed Properties

Arab Light Resid

Arab Heavy Resid

1,050 (965)
7.5
4.3
0.37
22.0
116

1,050 (965)
3.2
5.6
0.47
28.5
250

Nominal Cut point, F (C)

Density, API
Sulfur, wt%
Nitrogen, wt%
CCR, wt%
Metals, ppm w
Reactor Products, wt% on feed

Recycle

Once-Thru

Recycle

Once-Thru

11.2
15.3
12.1
34.7
0.0
26.7

9.8
13.3
10.7
30.0
12.3
23.9

12.9
14.4
10.2
27.1
0.0
35.4

11.2
12.5
8.9
24.1
12.2
31.1

Recycle

Once-Thru

Recycle

Once-Thru

Density, API
Sulfur, wt%
Nitrogen, wt%
H/C Weight Ratio

55.4
0.8
0.01
0.159

58.4
0.8
0.01
0.166

55.6
1.0
0.01
0.160

57.4
1.0
0.01
0.164

Light Gas Oil (430/650F; 220/345C)

Density, API
Sulfur, wt%
Nitrogen, wt%
H/C Weight Ratio

25.7
2.8
0.10
0.135

28.5
2.8
0.10
0.137

25.9
3.6
0.12
0.135

27.3
3.6
0.12
0.136

Heavy Gas Oil (650/975F; 345/525C)

Density, API
Sulfur, wt%
Nitrogen, wt%
CCR, wt%
Metals, ppm w
H/C Weight Ratio

10.6
4.3
0.4
3.8
1.6
0.120

13.4
4.3
0.4
3.8
1.6
0.124

10.5
5.6
0.6
4.9
3.4
0.120

12.2
5.6
0.5
4.9
3.4
0.122

5.9
4.5
0.4
18.6
53
0.098

0.3
5.9
0.5
24.1
113
0.096

C4 and lighter
C5/430F (C5/220C)
430/650F (220/345C)
650/975F (345/525C)
975F+ (525C+)
Gross Coke
Liquid Product Qualities
Naphtha (C5/430F; C5/220C)

Bottoms (975F+; 525C+)

Density, API
Sulfur, wt%
Nitrogen, wt%
CCR, wt%
Metals, ppm w
H/C Weight Ratio

02055_A_A

2008 ENSPM Formation Industrie - IFP Training

16

Table 5
FLUID COKING AND FLEXICOKING UNITS
Worldwide Commercial Fluid Coking/Flexicoking Units

Facility Owner's Name

Locations (Facility Name)

No. of
Trains

Operating
Cap.,
bbl/cd

Coke
Prod'n
mt/cd

Start
Year

8,000

375

Dec. 1954

Exxon. Expanded from 3.8 to

7.7 Mbbl/d. Coke & Burner flue
gas are burned in the adjacent
Yellowstone Energy LP 57 MW
cogen plant.

42,000

500

June 1957

Exxon. Produces medium-sulfur

coke (1.5-2.5 wt% S); coke sold
directly to GWF; Oxbow also
brokers some coke production
(150 Mt/yr).

Licensor/Comments

Commercial Fluid Coking

Units
ExxonMobil
Refining
&
Supply Co.
Billings, MT, United
States (Exxon Billings
Refinery)

Tersoro Petroleum Corp.

Martinez , CA, United States
(Golden Eagle (Avon)
Refinery)

Motiva Enterprises LLC

Delaware City, DE, United
States (Delaware City Plant)

47,000

1,700

Aug. 1957

Exxon. Expanded from 42 to

45 Mbbl/d; 2003 revamp is in
engineering by Belco. All of the
coke
production
is
now
consumed onsite by the new
Delaware Clean Power GCC
project employing Texaco POX
technology.

Amerada Hess Corp.

Purvis, MS, United States
(Purvis Refinery)

Dec. 1957

Exxon. 7.2 Mbbl/d coking train

shutdown with refinery in 1994
(design
rate
4.8 Mbbl/d);
produced 250 mt/d of coke when
unit last operated.

12,000

Feb. 1968

Exxon.
Expanded
from
10 Mbbl/d. Coke production is
shown with the DC-A unit.

23,300

850

April 1968

Exxon.
Expanded
14 Mbbl/d.

Petroleos Mexicanos
Tampico, Tamaulipas,
Mexico (Ciudad
Madero Refinery)
Imperial Oil Ltd
Sarnia, Ont., Canada
(Sarnia Refinery)

02055_A_A

2008 ENSPM Formation Industrie - IFP Training

from

17

Facility Owner's Name

Locations (Facility Name)

No. of
Trains

Operating
Cap.,
bbl/cd

Valero Energy Corps./Valero Refining & Marketing Co.

Benicia, CA, United
1
29,000
States (Benicia
Refinery)

Syncrude Canada Ltd.

Fort McMurray, Alb.,
Canada (Mildred
Lake Tar Sands
Upgrading Facility)

"

"

Total Fluid Coking Units

Commercial Flexicoking Units

Toa Oil Co. Ltd.
Kawasaki, Japan (Mizue
Factory)
Centro de Refinacion de
Paraguana
Judibana/Punta Cardon,
Falcon, Venezuela
(Amuay-Carbon Refinery)
Shell Oil Product US
Martinez, CA, United
States (Martinez
Manufacturing Complex)

02055_A_A

Coke
Prod'n
mt/cd

Start
Year

1,080

April 1969

Exxon.
Expanded
from
16 Mbbl/d. Coke is sold directly
by Valero to users; >50% fired by
GWF in Combustion Power FICIRCS hybrid FBC boilers @
GWF Power System facilities
(Antioch, Hanford, & Pittsburg,
CA); also sells coke to Taiheiyo
Cement in Japan.
Exxon. Each coking train @
107 Mbbl/d expanded from
design capacity of 73 Mbbl/d per
train (based on whole bitumen
feed). Processes atm. & vac.
topped bitumen and LC-Finer
bottoms.
Exxon. New 95 Mbbl/d fluid
coking train is being built as part
of $ 2.4 billion Upgrader
Expansion-1 (UE-1) project
added since Phase 6; to process
100% vac. topped bitumen; unit
to have significantly larger
reactor volume and coke holdup
than FLCA-B. To produce 1,5002,000 mt/d of coke.

Licensor/Comments

2
(FLC/A-B)

214,000

2,900

July 1978

0
(FLC-C)

1 Q 2005

375,300

8,405

24,000

150

Sept. 1976

Exxon. Expanded from 20.4 to

24 Mbbl/d.

57,600

Nov. 1982

Exxon. Coking train is situated

within the Amuay Refinery; 1990
expansion from 52 to 65 Mbbl/d;
the World's largest Flexicoker.

20,400

131

March 1983

Exxon. Design capacity of

22 Mbbl/d. Flexicoke (0.9 wt%S;
30 HGI) is marketed by Oxbow.

2008 ENSPM Formation Industrie - IFP Training

18

Operating
Cap.,
bbl/cd

Coke
Prod'n
mt/cd

Start
Year

39,000

300

Sept. 1986

38,000

382

Sept. 1986

Total Flexicoking Units

179,000

963

Total World

13

554,300

9,368

Facility Owner's Name

Locations (Facility Name)

No. of Trains

ExxonMobil Refining & Supply Co.

Rotterdam, Netherlands
(Rotterdam Refinery)
Baytown, TX, United
States (Baytown
Refinery)

02055_A_A

2008 ENSPM Formation Industrie - IFP Training

Licensor/Comments

Exxon. Expanded from 32 to

38 Mbbl/d.
Exxon.
Expanded
from
28 Mbbl/d. There are no plans to
use produced Flexicoke in
Baytown gasifier due to very low
(possibly zero) transfer price.

19

Table 6
HYDROTREATMENT OF FLUID COKING PRODUCTS

Naphtha
C5-170C

Middle distillate
67% ex fluid
coking 33% ex
HDT of heavy
Gas oil

CHARACTERISTICS

FEED

PRODUCTS

Specific Gravity
Gravity API
Sulfur wt%
Nitrogen ppm
Bromine N g/100 g

0.753
56.7
1.17
80
122

0.721
64.9
< 10-6
<1
<1

Diene value g/100 g

14

CHARACTERISTICS

FEED

PRODUCTS

Specific Gravity
GravityAPI
Sulfur wt%
Nitrogen ppm
Bromine N
MAV
Aromatics vol%
Cetane index

0.884
28.6
2.3
760
44
32
54
31

0.840
37
< 20.106
< 110
<1
0
20
52

CHARACTERISTICS

FEED

PRODUCTS

0.999
10.1
5.8
4.700
4
5.7

0.933
20.1
< .1
1100
< .1
0.3

Specific Gravity
Heavy Gasoil
Gravity API
(350-510C) from
Sulfur wt%
fluid coking
Nitrogen ppm
Metals ppm (Ni + V)
Conradson Carb wt%

02055_A_A

2008 ENSPM Formation Industrie - IFP Training

PROBLEMS ENCOUNTERED
Diolefins
Olefins
Si-As
Nitrogen

fouling

Strong heat release

PROBLEMS ENCOUNTERED
Diolefins
Olefins
Nitrogen
(Si-As)
Pericondensed aromatics
Heat release
H2 consumption

PROBLEMS ENCOUNTERED
Nitrogen
Pericondensed aromatics
Metals
(Sediments)

02055_A_A

.844
4.1
0.44
700
14
49
3
>8

Sp gr
Viscosity cSt 20C
Sulfur (wt%)
Total nitrogen (ppm)
Bromine N (g/100 g)
Cetane number
Color ASTM D 1500
Color Stability ASTM (D 2274)

2008 ENSPM Formation Industrie - IFP Training

Operating
ranges

P (MPa)
LHSV
TC

H2 Consumption/Feed (wt%)

Paraffins
(wt%)
Naphtenes
(wt%)
Total aromatics and thiophenics (wt%)

FEED

CHARACTERISTICS

<5
24
330 360

0.5

0.832
4.0
0.03
150
0.1
53
0.5
0.5

PRODUCT

DELAYED COKER GO
STABILIZATION

FEED OBJECTIVE

3.9
30.4
65.7

.945
14.2
3.9
1320
19
28
8

FEED

8 12
0.5 1.5
350 400

11
76
13

.850
4.5
36.106
<2
< 0.1
41
1

PRODUCT

FLUID COKER GO CETANE

IMPROVEMENT STABILIZATION

6-8
1-3
340-380

1.8

12.5
12.5
75

0.907
3.8
0.09
10
.1
27
< 0.5
< 0.5

0.958
4.9
2.3
530
14
20
2
5
7.1
5.6
87.3

PRODUCT
1

FEED

IFP RESULTS

8-12
0.5-1.5
350-390

3.6

8.3
65.7
26

0.862
3.4
30.106
1
< .1
40

PRODUCT
2

CAT-CRACKER LCO CETANE IMPROVEMENT

HYDROTREATMENT OF HIGHLY UNSATURATED GAS OILS

Table 7

20

FLEXICOKING - GASIFICATION
Simplified scheme

Figure 4

STEAM GENERATION
GASIFICATION
GAS

DESULFURIZATION

Coke
fines

Cracked
products

GAS

WASH
SECTION
Recycle

HEATER
1,7

620

GASOLINE

GASIFIER

REACTOR
490
530
750
980

VACUUM
RESIDUE
FEED

GAS OIL

Steam

DISTILLATE

Air

COMPRESSOR

Steam

Crude origin

Arabian light

PRODUCTS
GAS

YIELD ON 100 TONS

OF FEED
13.4

wt % on crude

19.3 %

GASOLINE

9.2

sp.gr

1.012

GAS OIL

20.7

S%

4.0

DISTILLATE

30.0

Conradson carbon wt %

20

COKE FINES

2.7

GASIFIED COKE

24.0

(1)

(2)

(1) Including 0.9 ton of H2S

(2) Coke burned in the gasifier producting a lean gas (LHV 900 kcal/Nm3) corresponding in quantity to 15.8% vol.
of feed in fuel oil equivalent

2008 ENSPM Formation Industrie - IFP Training

D PCD 322 B

VACUUM
RESIDUE FEED