CHAPTER 10

DELAYED COKING

Coking is by far the most widely practiced means of reducing the

carbon-hydrogen ratio of residual oils. Of the two main processes
delayed coking and fluid cokingthe bulk of the capacity (about
90%) is in delayed coking units.
Both processes have the dual purposes of increasing cat cracker
feedstock availability and of reducing the production of residual
fuel oil.
In delayed coking, carbon is removed in the form of a black
solid that is referred to as green coke. It contains moisture, volatile
combustible matter (VCM), sulfur, and metals concentrated from
the feed. Fixed carbon content ranges from 85% to 95%. After
roasting to reduce the moisture and VCM, typically in a rotary kiln,
the calcined coke contains 98% to 99.5% fixed carbon.1 The uses
and specifications of the various grades of coke will not be elabo-
rated on here.

Delayed coking process description

As shown in Figure 101, the fresh feed is introduced direct-
ly into the fractionator. This permits flashing of lowering boiling
material not desired in the furnace feed, combining remaining
fresh feed with recycle (if any), and preheating the feed to the fur-
nace. In the furnace, the endothermic heat of the coking reaction
is supplied in a way to minimize coking in the furnace itself. The
furnace effluent goes to a coke chamber where coke is formed

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Fig. 101 Simplified Delayed Flow Coking Scheme

and accumulates. Overhead vapors from the coke drum enter the lower
part of the fractionator to be separated into gas, naphtha, light and heavy
gas oils, and recycle.
While coke is being formed in one drum, coke is being removed from
another by highpressure water jets. Currently drum cycles range from 32
to 48 hours for a complete turnaround.
Coking is another of those processes where no finished fluid product
(liquid or vapor) is made. Every stream from the coker requires further
processing.

Delayed coking data correlation

The database for delayed coking yield correlation is displayed in Table
101. Again, there are many gaps in the table. The chief problem encoun-
tered with these data was the general lack of boiling ranges of cuts. The
terms distillate and gas oil are ambiguous in this respect, and gasoline can
vary in end point and be butanefree or not. The assumption was made that
the gasoline was butanefree (BFG) and had a 400F end point. Further, liq-
uid boiling above gasoline was considered gas oil (data labeled distillate and
gas oil were added together in the same set).

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Table 101a Delayed Coking Database

Following the procedure outlined previously, some of the results

obtained using first order relations are shown in Table 102. Coke yield
correlates very well with Conradson carbon residue content of feed. Gas,
gas oil, and C5+ correlate slightly better with coke yield than with

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Table 101b Delayed Coking Database contd

Conradson carbon residue. The gasoline data are very scattered in either
case with no strong definite trend indicated. It was decided to obtain gaso-
line yield by difference. Figure 102 is a composite plot of the yields.

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Table 102 Some Results of Delayed Coking Yields Correlations

Fig. 102 Delayed Coker Yields

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PETROLEUM REFINERY P ROCESS ECONOMICS

The butanes and lighter gas can be assumed to have approximately the
following composition in weight percent:

Hydrogen 0.9
Methane 27.2
Ethylene 6.7
Ethane 17.8
Propylene 10.8
Propane 14.4
Butylenes 11.0
Isobutane 2.4
Normal butane 8.8
Total 100.0

In the case of H2S, a second parameter, percent sulfur in feed, was used
along with weight percent coke yield as an independent variable. The result
is plotted in Figure 103. The weight percent contents of sulfur in coke,
gasoline, and gas oil are plotted in Figure 104.
A number of product properties was explored, including gasoline
octane, gasoline PONA, Conradson carbon residue content of gas oil, and
API and sulfur content of both gasoline and gas oil. There was insufficient
data to develop a relationship for gasoline octane, only to indicate a range
(RON of 61 to 68) in which it might fall. Of more significance, since the
gasoline requires further processing, is its PONA (average values of 40, 37,
13, 10). API gravity is important in making an overall material balance (Fig.
105). Conradson carbon residue is important for gas oil fed to a cat cracker
(Fig. 106). Too few data were found on nitrogen contents to be useful. A
plot of liquid volume percent vs. weight percent for coke products appears
in Figure 107.

Comparison with other correlations

Early attempts to correlate delayed coking yields used the API of the
feed as the independent variable as had been the practice with thermal
cracking. The results were not very good. George Armistead presented a

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Fig. 103 Delayed Coker Hydrogen Sulfide Yield

Fig. 104 Sulfur in Delayed Coker Products

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PETROLEUM REFINERY P ROCESS ECONOMICS

Fig. 105 Delayed Coker Product Gravities

Fig. 106 CCR in Delayed Coker Gas Oil (Wt% Yield of Coke Plus Gas is Parameter)

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Fig. 107 Lv% vs. Wt% of Coker Products

plot2 of gas, gasoline, and coke yields vs. API gravity of feedstock with a dis-
cussion of the various other variables at play in the process.
Nelson3 developed equations relating the volume percent yield of gaso-
line with the API gravity of the feed and with the volume yield and API
gravity of gas oil, along with tabulated yields calculated from these equa-
tions. In a later article,4 Nelson published coke and gas yields correspond-
ing with those gasoline yields. Still later,5 he published yields of coke in
terms of Conradson carbon residue content of feed (see comparison below).
Martin and Wills in Advances in Petroleum Chemistry and Refining,6
gave equations for coke and gas yields in terms of Conradson carbon
residue. Jakob7 published a curve for coke yield in terms of Conradson car-
bon residue that appears to be a plot of a third order equation. Gary and
Handwerk (G & H)8 presented equations for coke, gas, and gasoline yields
with gas oil obtained by difference.
The following tabulation shows how some of these relationships com-
pare with those developed by the author:

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PETROLEUM REFINERY P ROCESS ECONOMICS

Coke Yield
WT%
Conradson Author Nelson M&W Jakob G&H
carbon residue
5 8.2 8.5 10.3 15 8
10 16.4 18 18.6 20 16
15 24.6 27.5 26.9 29 24
20 32.7 35.5 35.2 36 32
25 40.9 42 43.5 40

G & H state that their relationships are based on straightrun residuals as

are those of the author. It is not known if this is true for the others.
Attempts at deriving a simple correlation for gasoline yields were so
discouraging it was decided to obtain them by difference.
A comparison of the authors results with G & Hs gas yields appears
in the following tabulation:

WT% Conradson G&H Author

carbon residue
5 8.52 5.47
10 9.24 6.87
15 9.96 8.27
20 10.68 9.67
25 11.40 11.07
30 12.12 12.47

It is assumed that the differences in results are due to differences in the

data populations employed in the correlations. Such an explanation may
account for the differences found between the authors results for sulfur
content of coke and that of others. Though the authors regression results
look good they are higher than those reported by others:

Feed S Author Nelson9 Kutler10 Jakob7

0.25 0.5
0.9 1.5

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Feed S Author Nelson9 Kutler10 Jakob7

1 1.4 1.2 0.7
2 2.8 2.1 1.42
3 4.2 3.2 2.53.1
4 5.6 4.4 3.84.3
5 7 5.7 5 5.55.8
6 8.4 7.2 7.5

Jakob used Conradson carbon residue of feed as a second independent

variable. Nelsons values are averages. He commented that he observed
greater variation than Jakob. For the authors data, the improvement in
adding Conradson carbon residue as a parameter was not significant.
Kutler, et al., point out that certain California crudes produce cokes with
significantly lower sulfur content than would be expected from the feed
sulfur content.10
G & H give percentages for the distribution of sulfur and nitrogen in
the feed to the various products. As stated previously, the author did not
find sufficient nitrogen data to work with. Results on sulfur are summarized
here as percent of sulfur in feed appearing in product:

G&H Author Average Range

Gas 30 14.9 6.335.7
Gasoline 5 3.3 2.35.5
Gas oil 35 33.5 1242
Coke 30 29.7 15.650.2

It is recommended that Figures 103 and 104 be used rather than

authors average values above.

Delayed coking operating requirements

The following data are for the continuous operation of the coking pro-
cess. There is an increase in steam requirement during the purging of the
drum before and after decoking and in electric power during decoking.

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PETROLEUM REFINERY P ROCESS ECONOMICS

Electric power, kWh/b 3.6

Fuel, mBtu/b 120
Cooling water, gpm/b/h 0.6
High pressure steam, #/b < 40 >

Delayed coker capital cost

Eight published capital costs for delayed cokers were adjusted to
20,000 BPD and January 1991 with an average result of $46 million (rang-
ing from 40.7 to 51.3).

Notes
1. Reis, T., Hydrocarbon Processing, June 1975, pp. 97104

2. Armistead, G., Jr., Oil & Gas Journal, March 16, 1946, pp.
103111

3. Nelson, W.L., Oil & Gas Journal, July 7, 1952, p. 103

4. Ibid, February 15, 1954, p. 181

5. Ibid, January 14, 1974, p. 70

6. Martin, S.W., and Wills, L.E., Advances in Petroleum Chemistry

and Refining, Vol. 2, Interscience Publishers Inc., New York,
1959, pp. 364419

7. Jakob, R.R., Hydrocarbon Processing, September 1971, pp.

132136

8. Gary, J.H., and Handwerk, G.E., Petroleum Refining Technology

and Economics, Marcel Dekker, New York, 2nd ed., 1984

9. Nelson, W.L., Oil & Gas Journal, Oct. 9, 1978, p. 71

10. Kutler, A.A., DeBiase, R., Zahnstecher, L.W., and Godino, R.L.,
Oil & Gas Journal, April 5, 1970, pp. 9296

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References
DeBiase, R., and Elliott, J.D., Oil & Gas Journal, April 19, 1982, pp.
8188

Foster, A.L., Petroleum Engineer, April 1951, pp. C53 to C62

Gibson, C.E., Refining Engineer, April, 1958, pp. C46 to C50

Heck, S.B., Oil & Gas Journal, July 24, 1972, pp. 4648

Hengstebek, R.J., Petroleum Processing, McGrawHill Book Co.,

New York City, 1959, p. 142

Jakob, R.R., Hydrocarbon Processing, September 1971, pp. 132136

Kutler, A.A., DeBiase, R., Zahnstecher, L.W., and Godino, R.L., Oil
& Gas Journal, April 5, 1970, pp. 9296

Mekler, V., and Brooks, M.E., Petroleum Refiner, Vol. 39, No. 2,
1960, ff. 158

Meyer, D.B., and Webb, H.C., Petroleum Refiner, Vol. 39, No. 2,
1960, pp. 155158

Meyers, R.A., Handbook of Petroleum Refining Processes,

McGrawHill Book Co., New York City, 1986, pp. 718, 725,
726

Mohammed, AH.A.K., Abdullah, M.O., and AbdulAmmer, A.A.,

Hydrocarbon Processing, November 1979, pp. 66F to 66L

Murphy, J.R., Whittington, E.L., and Chang, C.P., Hydrocarbon

Processing, September 1979, pp. 119122

Nelson, W.L., Oil & Gas Journal, July 7, 1952, p. 103

Ibid, March 9, 1953, pp. 125126

Ibid, March 23, 1953, p. 359

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PETROLEUM REFINERY P ROCESS ECONOMICS

Ibid, February 15, 1954, p.181

Ibid, November 28, 1955, p. 117

Ibid, February 25, 1963, p. 115

Ibid, January 14, 1974, p. 70

Ibid, October 9, 1978, p. 71

Ibid, December 18, 1978, pp. 6869

Reis, T., Hydrocarbon Processing, June 1975, pp. 97104

Rose, K.E., Hydrocarbon Processing, July 1971, pp. 8592

Stolfa, F., Hydrocarbon Processing, May 1980, pp. 101109

152