Delayed Coking

Chapter 5

1
 Gasses

Polymer- Sulfur
ization Plant
Sulfur

LPG
Sat Gas
Gas Plant
Alkyl Butanes Fuel Gas
Feed
LPG
Alkylation

Gas Polymerization
Separation & Naphtha
Stabilizer Isom-
erization
Isomerate
Light Naphtha Alkylate
Aviation
Gasoline
Automotive
Gasoline
Reformate
Naphtha Solvents
Heavy Naphtha
Hydro-
Naphtha Reforming
treating Naphtha
Atmospheric
Distillation

Jet Fuels
Kerosene
Crude
Desalter Kerosene
Oil
Cat Solvents
Distillate Hydro-
AGO Naptha Distillate
cracking Treating &
Hydro-
Blending
Heating Oils
Gas Oil Fluidized treating
LVGO Hydro- Catallytic Diesel
treating Cracking
Cat
Vacuum Distillates
Distillation HVGO
Fuel Oil
Cycle Oils
Residual
DAO Fuel Oils

Solvent
Coker SDA
Deasphalting
Naphtha Bottoms Naphtha Asphalts

Visbreaking Distillates
Fuel Oil
Bottoms
Coker Lubricant
Vacuum Residuum Lube Oil
Gas Oil
Solvent Greases
Dewaxing
Waxes
Waxes
Coking
Coke

2
 Delayed Coking
Purpose

Feedstock

Products

Underlying
Principles
Configuration

Other
Characteristics

3
 Purpose
• Process heavy residuum to produce distillates
(naphtha & gas oils) that may be catalytically
upgraded
» Hydrotreating, catalytic cracking, and/or
hydrocracking
• Attractive for heavy residuum not suitable for
catalytic processes
» Large concentrations of resins, asphaltenes, &
heteroatom compounds (sulfur, nitrogen,
oxygen, metals)
• Metals, sulfur, & other catalyst poisons
generally end up in coke
» Sold for fuel & other purposes
• Carbon rejection process

4
Characteristics of Petroleum Products

5
 Development of Coking

• After World War II railroads shifted from steam to diesel

locomotives
» Demand for heavy fuel oil sharply declined
» Coking increases distillate production & minimizes heavy fuel oil
• 1950 to 1970 coking capacity increased five fold
» More than twice the rate of increase in crude distillation capacity
» Increase in heavy high sulfur crude combined decrease in heavy fuel
oil

6
 Development of Coking

• Coking capacity is measured in terms of both coke production in

tons per day & residual oil feed rate in barrels per day
• 2008 EIA database:

Unit bbl/day Relative Capacity

Crude Units 18.8 MMbpd —
Vacuum Units 8.7 MMbpd 46%
Delayed Coking
2.4 MMbpd 13%
Units
Fluid Coking Units 0.2 MMbpd 1%

7
 Coking Chemistry
• “Carbon rejection” process
» Coke has very little hydrogen – shifts to the lighter products
» Metals (hydrotreating catalyst poisons) concentrate in coke
• Cycle of cracking & combining
» Side chains cracked off of PNA (Polynuclear Aromatic) cores

Heteroatoms in side chains end up in light products
» PNAs combine (condense) to form asphaltenes & coke

Metals & heteroatoms in PNA cores end up in coke
• Conditions
» High temperatures & low pressures favor cracking

More distillate liquids

Lower yields of coke & hydrocarbon gas
» High residence time favor the combining reactions
» Over conversion will reduce distillates & produce coke and hydrocarbon gases

8
 Delayed Coking

• Predominate coking technology

• Delayed Coking technology is relatively inexpensive
» Considered open art
» Companies do license technology emphasizing coke furnaces, special
processing modes, & operations

9
 Feed for the Delayed Coker

• Delayed Coker can process a wide variety of feedstocks

» Can have considerable metals (nickel & vanadium), sulfur, resins, &
asphaltenes
» Most contaminants exit with coke
• Typical feed is vacuum resid
» Atmospheric resid occasionally used
• Typical feed composition
» 6% sulfur
» 1,000 ppm (wt) metals
» Conradson Carbon Residue (CCR) of 20-30 wt%
• Feed ultimately depends on type of coke desired

10
 Solid Products

• Coke with large amounts of metals & sulfur may pose a disposal
problem
» Refiner may have to pay for disposal
• Product grades
» Needle coke

Used for electrodes in steel manufacturing
» Anode grade

Used for electrodes in aluminum production
» Fuel grade

About 85% carbon & only 4% hydrogen

11% heteroatoms: sulfur, nitrogen, oxygen, vanadium & nickel
» Shot coke

Operational problems

11
 Solid Products

• Hydroprocessing upstream of delayed coker may be used to make

high quality coke
• Needle coke
» FCC cycle oils, gas oils, & resids with low sulfur & aromatics used as
feedstocks
» Used for electrodes in steel manufacturing
• Anode grade coke
» Resids with small ring aromatics
» Used for electrodes in aluminum production

12
 Solid Products

• Fuel grade coke

» About 85% carbon & only 4% hydrogen
» 11% heteroatoms sulfur, nitrogen, oxygen, vanadium & nickel
» Resid high in polynuclear aromatics & sulfur used as feedstock
• Shot coke
» From size of small ball bearings to golf ball
» Nearly always try to avoid!

Little market

Operational problems

13
“Shot Coke: Design & Operations,” John D. Elliott
http://www.fwc.com/publications/tech_papers/oil_gas/shotcoke.pdf

14
15
 Light Products

• Vapor light ends processed in coker gas plant.

• Liquids
» Naphtha fraction may be used as catalytic reformer feed after
hydroprocessing

Only small fraction of gasoline pool
» Gas oil fed to catalytic cracker or hydrocracker

Hydrocracker preferred — does better job of processing aromatic
rings
• Reduced aromatics & heteroatoms concentrated in coke, but still
contain large amounts of sulfur & olefins

16
 Feedstock Selection
• Amount of coke related to carbon residue of feed
» Correlates to hydrogen/carbon ratio & indicates coking tendency
• Three main tests

Conradson Carbon (ASTM D 189)

Ramsbottom method (ASTM D 524)

Microcarbon Residue Test (ASTM D 4530 )

17
 Yields

•Low yields of liquids relative to hydrocracking

» Mass conversion of vacuum resids to liquids about 55% — about 90%
for hydrocracking
•Coke & liquid yields may be estimated by simple equations
(misprint pg. 75 — see pg. 89)

Coke Yield (wt%) = 1.6 × (wt% CCR)

Gas (C4-) (wt%) = 7.8 + 0.144 × (wt% CCR)
Gasoline (wt%) = 11.29 + 0.343 × (wt% CCR)
Gas Oil (wt%) = 100 - (wt% Coke) - (wt% Gas) - (wt% Gasoline)
186.5
Gasoline (vol%) = × (wt% Gasoline )
131.5 + °API
155.5
Gas Oil (vol%) = × (wt% Gas Oil)
131.5 + °API

18
 Product Light Ends & Sulfur Distribution

• Estimated product distribution — Tables 5.8 & 5.9

Typical Gas Composition Typical Distributions
Component Mole% Sulfur (%) Nitrogen (%)
Methane 51.4
Gas 30 —
Ethene 1.5
Light
Ethane 15.9 1.7
Naphtha
Propene 3.1 Heavy
3.3 1
Propane 8.2 Naphtha
Butenes 2.4 LCGO 15.4 2
I-Butane 1.0 HCGO 19.6 22
N-Butane 2.6 Coke 30 75
H2 13.7
Total 100 100
CO2 0.2
Total 100.0

19
 Use of Yield Equations
Liq Vol% Wt% Mol% Std Liq Density Mol Wt
H2 Calc 13.7 * Pure
H2S Calc * Pure Pure
CO2 Calc 0.2 Pure Pure
C1 Calc 51.4 Pure

7.8 + 0.144 * %CCR

C2= Calc 1.5 Pure Pure
Gas (C4-)

C2 Calc 15.9 Pure Pure

C3= Calc 3.1 Pure Pure
C3 Calc 8.2 Pure Pure
C4=s Calc 2.4 Pure Pure
IC4 Calc 1.0 Pure Pure
NC4 Calc 2.6 Pure Pure

(Wt%) * 186.5 / (131.5 11.29 +

Gasoline Calculate
+ °API) 0.343 * %CCR
(wt%)* 155.5 / (131.5
Gas Oil ∆ Calculate
+ °API)

Coke 1.6 * %CCR

Total 100% 100%

Notes:
• Sulfur in gas as H2S. Decrease H2 amount to account for amount H2S.
• Interrelate the mass of non-sulfur gas using the mol% values above.

20
 Example Yield Problem #1

• What are the expected products from a delayed coker when

running 100,000 sbpd of the Torrance Field crude oil (assay on
page 404)? Use the residuum as given in assay .

21
 Example Yield Problem #1
CCR Sulfur (wt%) Yield Yield
bbl/day lb/day SpGr lb/gal °API wt% wt% wt% vol%
Crude Charge 100,000 31,899,718 0.9110 7.595 23.8
Vac Resid Feed 1.0040 8.371 9.4 13.20 2.89 41.9
Coker Gas
Coker Gasoline
Coker Gas Oil
Coke
Coker Total 0.00

Suflur Distribution Coker Gas Composition

Sulfur (%) lb/day mol/day Corrected Corrected Corrected
Gas 30.0 0 Component Mol% Mol Wt mol/day mol/day Mol% lb/day
Light Naphtha 1.7 Methane 51.4 16.043
Heavy Naphtha 3.3 Ethene 1.5 28.054
LCGO 15.4 Ethane 15.9 30.070
HCGO 19.6 Propene 3.1 42.081
Coke 30.0 Propane 8.2 44.097
Total 100.0 Butenes 2.4 56.108
I-Butane 1.0 58.123
N-Butane 2.6 58.123
H2 13.7 2.016
CO2 0.2 44.010
H2S 34.080
Sulfur 32.064
Total 100.0
w/o Sulfur 22.171

22
 Example Yield Problem #1
CCR Sulfur (wt%) Yield Yield
bbl/day lb/day SpGr lb/gal °API wt% wt% wt% vol%
Crude Charge 100,000 31,899,718 0.9110 7.595 23.8
Vac Resid Feed 41,900 1.0040 8.371 9.4 13.20 2.89 41.9
Coker Gas
Coker Gasoline
Coker Gas Oil
Coke
Coker Total 0.00

Suflur Distribution Coker Gas Composition

Sulfur (%) lb/day mol/day Corrected Corrected Corrected
Gas 30.0
Light Naphtha 1.7
Determine volume0 feed
Component
Methane
based Mol%51.4 Mol Wt
16.043
mol/day mol/day Mol% lb/day

Heavy Naphtha 3.3 on vol% yield of vacuum

Etheneresid. 1.5 28.054
LCGO 15.4 Ethane 15.9 30.070
HCGO 19.6 Propene 3.1 42.081
Coke 30.0 Propane 8.2 44.097
Total 100.0 Butenes 2.4 56.108
I-Butane 1.0 58.123
N-Butane 2.6 58.123
H2 13.7 2.016
CO2 0.2 44.010
H2S 34.080
Sulfur 32.064
Total 100.0
w/o Sulfur 22.171

23
 Example Yield Problem #1
CCR Sulfur (wt%) Yield Yield
bbl/day lb/day SpGr lb/gal °API wt% wt% wt% vol%
Crude Charge 100,000 31,899,718 0.9110 7.595 23.8
Vac Resid Feed 41,900 14,730,456 1.0040 8.371 9.4 13.20 2.89 46.2 41.9
Coker Gas
Coker Gasoline
Coker Gas Oil
Coke
Coker Total 0.00

Suflur Distribution Coker Gas Composition

Sulfur (%) lb/day mol/day Corrected Corrected Corrected
Gas 30.0 0 Component Mol% Mol Wt
Light Naphtha 1.7
Determine mass
Methane
feed
51.4
based on mol/day
16.043
mol/day Mol% lb/day

Heavy Naphtha 3.3 density of vacuum

Ethene 1.5 resid.
28.054
LCGO 15.4 Ethane 15.9 30.070
HCGO 19.6 Propene 3.1 42.081
Coke 30.0 Propane 8.2 44.097
Total 100.0 Butenes 2.4 56.108
I-Butane 1.0 58.123
N-Butane 2.6 58.123
H2 13.7 2.016
CO2 0.2 44.010
H2S 34.080
Sulfur 32.064
Total 100.0
w/o Sulfur 22.171

24
 Example Yield Problem #1
CCR Sulfur (wt%) Yield Yield
bbl/day lb/day SpGr lb/gal °API wt% wt% wt% vol%
Crude Charge 100,000 31,899,718 0.9110 7.595 23.8
Vac Resid Feed 41,900 14,730,456 1.0040 8.371 9.4 13.20 2.89 46.2 41.9
Coker Gas 9.70
Coker Gasoline 15.82 20.93
Coker Gas Oil 53.36 58.88
Coke 21.12
Coker Total 100.00

Suflur Distribution Coker Gas Composition

Sulfur (%) lb/day mol/day Corrected Corrected Corrected
Gas 30.0 0 Component Mol% Mol Wt mol/day mol/day Mol% lb/day
Light Naphtha 1.7 Methane 51.4 16.043
Heavy Naphtha 3.3 Ethene 1.5 28.054
LCGO 15.4 Ethane 15.9 30.070
HCGO 19.6 Propene
Determine
3.1
yield42.081
percentages
Coke 30.0 Propane based on
8.2formulas.
44.097 Gas Oil
Total 100.0 Butenes Yield is calculated
2.4 by difference
56.108
I-Butane 1.0 58.123
from 100%.
N-Butane 2.6 58.123
H2 13.7 2.016
CO2 0.2 44.010
H2S 34.080
Sulfur 32.064
Total 100.0
w/o Sulfur 22.171

25
 Example Yield Problem #1
CCR Sulfur (wt%) Yield Yield
bbl/day lb/day SpGr lb/gal °API wt% wt% wt% vol%
Crude Charge 100,000 31,899,718 0.9110 7.595 23.8
Vac Resid Feed 41,900 14,730,456 1.0040 8.371 9.4 13.20 2.89 46.2 41.9
Coker Gas 1,428,972 9.70
Coker Gasoline 8,770 2,330,005 15.82 20.93
Coker Gas Oil 24,669 7,860,407 53.36 58.88
Coke 3,111,072 21.12
Coker Total 14,730,456 100.00

Suflur Distribution Coker Gas Composition

Sulfur (%) lb/day mol/day Corrected Corrected Corrected
Gas 30.0 0 Component Mol% Mol Wt mol/day mol/day Mol% lb/day
Light Naphtha 1.7 Methane 51.4 16.043
Heavy Naphtha 3.3 Ethene 1.5 28.054
LCGO 15.4 Ethane 15.9 30.070
HCGO 19.6 Propene 3.1 42.081
Coke 30.0 Propane 8.2 44.097
Total 100.0 Butenes 2.4 56.108
I-Butane 1.0 58.123
N-Butane 2.6 58.123
H2 13.7 2.016
Determine amountsCO2
based on 0.2 44.010
yield percentages.
H2S 34.080
Sulfur 32.064
Total 100.0
w/o Sulfur 22.171

26
 Example Yield Problem #1
CCR Sulfur (wt%) Yield Yield
bbl/day lb/day SpGr lb/gal °API wt% wt% wt% vol%
Crude Charge 100,000 31,899,718 0.9110 7.595 23.8
Vac Resid Feed 41,900 14,730,456 1.0040 8.371 9.4 13.20 2.89 46.2 41.9
Coker Gas 1,428,972 9.70
Coker Gasoline 8,770 2,330,005 0.7587 6.326 55.0 15.82 20.93
Coker Gas Oil 24,669 7,860,407 0.9100 7.587 24.0 53.36 58.88
Coke 3,111,072 21.12
Coker Total 14,730,456 100.00

Suflur Distribution Coker Gas Composition

Sulfur (%) lb/day mol/day Corrected Corrected Corrected
Gas 30.0 0 Component Mol% Mol Wt mol/day mol/day Mol% lb/day
Light Naphtha 1.7 Methane 51.4 16.043
Heavy Naphtha 3.3 Ethene 1.5 28.054
LCGO 15.4 Ethane 15.9 30.070
HCGO 19.6 Propene 3.1 42.081
Coke 30.0 Propane 8.2 44.097 Determine densities based on
Total 100.0 Butenes 2.4 56.108 volumes & mass produced.
I-Butane 1.0 58.123
N-Butane 2.6 58.123
H2 13.7 2.016
CO2 0.2 44.010
H2S 34.080
Sulfur 32.064
Total 100.0
w/o Sulfur 22.171

27
 Example Yield Problem #1
CCR Sulfur (wt%) Yield Yield
bbl/day lb/day SpGr lb/gal °API wt% wt% wt% vol%
Crude Charge 100,000 31,899,718 0.9110 7.595 23.8
Vac Resid Feed 41,900 14,730,456 1.0040 8.371 9.4 13.20 2.89 46.2 41.9
Coker Gas 1,428,972 9.70
Coker Gasoline 8,770 2,330,005 0.7587 6.326 55.0 15.82 20.93
Coker Gas Oil 24,669 7,860,407 0.9100 7.587 24.0 53.36 58.88
Coke 3,111,072 21.12
Coker Total 14,730,456 100.00

Suflur Distribution Coker Gas Composition

Sulfur (%) lb/day mol/day Corrected Corrected Corrected
Gas 30.0 127,713 3,983 Component Mol% Mol Wt mol/day mol/day Mol% lb/day
Light Naphtha 1.7 7,237 Methane 51.4 16.043
Heavy Naphtha 3.3 14,048 Ethene 1.5 28.054
LCGO 15.4 65,559 Ethane 15.9 30.070
HCGO 19.6 83,439 Propene 3.1 42.081
Coke 30.0 127,713 Propane 8.2 44.097
Total 100.0 425,710 Butenes 2.4 56.108
I-Butane 1.0 58.123
N-Butane 2.6 58.123
H2 13.7 2.016
CO2 0.2 44.010
Determine
H2S the distribution of 34.080
sulfur based on the typical 32.064
Sulfur
Total 100.0
factors.
w/o Sulfur 22.171

28
 Example Yield Problem #1
CCR Sulfur (wt%) Yield Yield
bbl/day lb/day SpGr lb/gal °API wt% wt% wt% vol%
Crude Charge 100,000 31,899,718 0.9110 7.595 23.8
Vac Resid Feed 41,900 14,730,456 1.0040 8.371 9.4 13.20 2.89 46.2 41.9
Coker Gas 1,428,972 8.94 9.70
Coker Gasoline 8,770 2,330,005 0.7587 6.326 55.0 0.009 15.82 20.93
Coker Gas Oil 24,669 7,860,407 0.9100 7.587 24.0 0.019 53.36 58.88
Coke 3,111,072 4.11 21.12
Coker Total 14,730,456 100.00

Suflur Distribution Coker Gas Composition

Sulfur (%) lb/day mol/day Corrected Corrected Corrected
Gas 30.0 127,713 3,983 Component Mol% Mol Wt mol/day mol/day Mol% lb/day
Light Naphtha 1.7 7,237 Methane 51.4 16.043
Heavy Naphtha 3.3 14,048 Ethene 1.5 28.054
LCGO 15.4 65,559 Ethane 15.9 30.070
HCGO 19.6 83,439 Propene 3.1 42.081
Coke 30.0 127,713 Propane 8.2 44.097 Scale the sulfur content of the
Total 100.0 425,710 Butenes 2.4 56.108
I-Butane 1.0 58.123
products as wt%.
N-Butane 2.6 58.123
H2 13.7 2.016
CO2 0.2 44.010
H2S 34.080
Sulfur 32.064
Total 100.0
w/o Sulfur 22.171

29
 Example Yield Problem #1
CCR Sulfur (wt%) Yield Yield
bbl/day lb/day SpGr lb/gal °API wt% wt% wt% vol%
Crude Charge 100,000 31,899,718 0.9110 7.595 23.8
Vac Resid Feed 41,900 14,730,456 1.0040 8.371 9.4 13.20 2.89 46.2 41.9
Coker Gas 1,428,972 8.94 9.70
Coker Gasoline 8,770 2,330,005 0.7587 6.326 55.0 0.009 15.82 20.93
Coker Gas Oil 24,669 7,860,407 0.9100 7.587 24.0 0.019 53.36 58.88
Coke 3,111,072 4.11 21.12
Coker Total 14,730,456 100.00

Suflur Distribution Coker Gas Composition

Sulfur (%)
lb/day mol/day Corrected Corrected Corrected
Gas 30.0127,713 3,983 Component Mol% Mol Wt mol/day mol/day Mol% lb/day
Light Naphtha 1.7 7,237 Methane 51.4 16.043 30,167
Heavy Naphtha 3.314,048 Ethene 1.5 28.054 880
LCGO 15.4 65,559 Ethane 15.9 30.070 9,332
HCGO 19.6 83,439 Propene 3.1 42.081 1,819
Coke 30.0127,713 Propane 8.2 44.097 4,813
Total 100.0425,710 Butenes 2.4 56.108 1,409
I-Butane 1.0 58.123 587
Split up the non-sulfur portion N-Butane 2.6 58.123 1,526
of the coker gas according to H2 13.7 2.016 8,041
CO2 0.2 44.010 117
the typical composition. H2S 34.080
Sulfur 32.064 3,983
Total 100.0 62,674
w/o Sulfur 22.171 58,691

30
 Example Yield Problem #1
Correct for presence of sulfur. CCR Sulfur (wt%) Yield Yield
bbl/day lb/day SpGr lb/gal °API wt% wt% wt% vol%
Crude Charge
Reduce the moles
100,000 31,899,718
of H replace
0.91102 7.595 23.8
Vac Resid Feed with
41,900 appropriate
14,730,456 amount of8.371
1.0040 9.4 13.20 2.89 46.2 41.9
Coker Gas 1,428,972 H2S. 8.94 9.70
Coker Gasoline 8,770 2,330,005 0.7587 6.326 55.0 0.009 15.82 20.93
Coker Gas Oil 24,669 7,860,407 0.9100 7.587 24.0 0.019 53.36 58.88
Coke 3,111,072 4.11 21.12
Coker Total 14,730,456 100.00

Suflur Distribution Coker Gas Composition

Sulfur (%) lb/day mol/day Corrected Corrected Corrected
Gas 30.0 127,713 3,983 Component Mol% Mol Wt mol/day mol/day Mol% lb/day
Light Naphtha 1.7 7,237 Methane 51.4 16.043 30,167 30,167 51.4 483,962
Heavy Naphtha 3.3 14,048 Ethene 1.5 28.054 880 880 1.5 24,697
LCGO 15.4 65,559 Ethane 15.9 30.070 9,332 9,332 15.9 280,604
HCGO 19.6 83,439 Propene 3.1 42.081 1,819 1,819 3.1 76,562
Coke 30.0 127,713 Propane 8.2 44.097 4,813 4,813 8.2 212,220
Total 100.0 425,710 Butenes 2.4 56.108 1,409 1,409 2.4 79,032
I-Butane 1.0 58.123 587 587 1.0 34,113
N-Butane 2.6 58.123 1,526 1,526 2.6 88,694
H2 13.7 2.016 8,041 4,058 6.9 8,180
CO2 0.2 44.010 117 117 0.2 5,166
H2S 34.080 3,983 6.8 135,742
Sulfur 32.064 3,983
Total 100.0 62,674 58,691 100.0 1,428,972
w/o Sulfur 22.171 58,691

31
 Example Yield Problem #1
CCR Sulfur (wt%) Yield Yield
bbl/day lb/day SpGr lb/gal °API wt% wt% wt% vol%
Crude Charge 100,000 31,899,718 0.9110 7.595 23.8
Vac Resid Feed 41,900 14,730,456 1.0040 8.371 9.4 13.20 2.89 46.2 41.9
Coker Gas 1,428,972 8.94 9.70
Coker Gasoline 8,770 2,330,005 0.7587 6.326 55.0 0.009 15.82 20.93
Coker Gas Oil 24,669 7,860,407 0.9100 7.587 24.0 0.019 53.36 58.88
Coke 3,111,072 4.11 21.12
Coker Total 14,730,456 100.00

Suflur Distribution Coker Gas Composition

Sulfur (%) lb/day mol/day Corrected Corrected Corrected
Gas 30.0 127,713 3,983 Component Mol% Mol Wt mol/day mol/day Mol% lb/day
Light Naphtha 1.7 7,237 Methane 51.4 16.043 30,167 30,167 51.4 483,962
Heavy Naphtha 3.3 14,048 Ethene 1.5 28.054 880 880 1.5 24,697
LCGO 15.4 65,559 Ethane 15.9 30.070 9,332 9,332 15.9 280,604
HCGO 19.6 83,439 Propene 3.1 42.081 1,819 1,819 3.1 76,562
Coke 30.0 127,713 Propane 8.2 44.097 4,813 4,813 8.2 212,220
Total 100.0 425,710 Butenes 2.4 56.108 1,409 1,409 2.4 79,032
I-Butane 1.0 58.123 587 587 1.0 34,113
N-Butane 2.6 58.123 1,526 1,526 2.6 88,694
H2 13.7 2.016 8,041 4,058 6.9 8,180
CO2 0.2 44.010 117 117 0.2 5,166
H2S 34.080 3,983 6.8 135,742
Sulfur 32.064 3,983
Total 100.0 62,674 58,691 100.0 1,428,972
w/o Sulfur 22.171 58,691

32
 Configuration

• Typical equipment
» Heater (furnace)
» Coke drum vessels
» Fractionator
» Downstream vapor processing vessels
• Coke drums run in two batch modes
» Filling
» Decoking
• Both modes of operation concurrently
feed to the fractionator

33
 Typical Delayed Coking Unit

Source:
Refining Overview – Petroleum Processes & Products,
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD-ROM, 2000

34
Typical Delayed Coking Unit

Fresh Feed & Furnace

• Fresh feed to bottom of

fractionator
• Total feed (fresh feed + recycle)
heated in furnace

35
Typical Delayed Coking Unit

Furnace

• Outlet temperature about 925°F

– cracking starts about 800°F
• Endothermic reactions
• Superheat allows cracking
reactions to continue in coke
drums– “Delayed Coking”

36
Typical Delayed Coking Unit
Furnace

• Steam injected into furnace

• Reduce oil partial pressure &
increase vaporization
• Maintains high fluid
velocities
• Wash on tube walls –
minimize coking in tubes

37
Typical Delayed Coking Unit

Coke Drum Configuration

• Flow up from bottom

• Coke solidifies & precipitates in
the drum
• Vapors out top of drum to
fractionator
• Even number of coke drums
• Typically two or four
• On-line coking step & other
set being decoked

38
Typical Delayed Coking Unit

Fill Coke Drum

• Coking reaction in drums & solid

coke deposited
• About 3 hours to fully
solidify
• Gas from top of coke drum to
fractionator
• Full cycle time till coke drum full

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Typical Delayed Coking Unit

Decoking

• Off-line drum decoked

• Quench step — hot coke
quenched with water giving off
steam & volatile hydrocarbons
• Vapors fed to the fractionator
• Coke drilled out with water drills

40
Typical Delayed Coking Unit

Coke Collection Systems

• Direct discharge to hopper car

• Pad loading
• Pit & crane loading
• Slurry loading

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http://www.glcarbon.com/ref/delayed.PDF

42
 Coke Drum Schedule

Drum Being Filled Drum Being Decoked

1 hour - Steam out

4 hours - Quench

1.5 hours - Dehead

16 hours - Fill drum with coke
4 hours - Drill out coke

1 hour - Rehead

4.5 hours - Test & Warmup

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 Decoking
• Each coke drum has a drilling rig that
raises & lowers a rotating cutting head
» Uses high-pressure (4,000 psig) water
• Steps
» Drum cooled & displaced with water to
remove volatiles
» Pilot hole is drilled through the coke to
bottom head
» Pilot drill bit replaced with a much larger
high-pressure water bit
» Cut either from top to bottom or bottom
to top
» The coke falls from coke drum into a
collection system

http://www.shellpsr.com/clients/tanker/34823.jpg

44
 Decoking

Handbook of Petroleum Refining Processes

Robert Meyers
McGraw-Hill, Inc, 1986

45
 Decoking

Handbook of Petroleum Refining Processes

Robert Meyers
McGraw-Hill, Inc, 1986

46
 Typical Delayed Coking Unit
Fractionator

• Vapors compressed & sent to

gas plant
• Naphtha is condensed from
fractionator overhead
• Gas oils are sidestream draws
from the fractionator
• Cycle oils internally recycled

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 Coke Products

• Green Coke — coke produced directly by a refinery

• Sub-classifications
» Needle coke

Produced from low sulfur & highly aromatic feeds
» Sponge coke

Largest production from the delayed coker

Term comes from its porosity
» Shot coke

Less desirable coke

Shot coke is a spheroid with diameters from 1 to 300 millimeters

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 Calcining

• Green coke heated to finish carbonizing coke & reduce volatile

matter to very low levels
» Calcining done in rotary kiln or rotary hearth
» Heated 1800 – 2400°F Calcining does not remove metals
» About ½ of green coke is calcined
• Uncalcined sponge coke has heating values of 14,000 Btu/lb
» Primarily used for fuel
» Crushed & drained of free water — contains 10% moisture, 10%
volatiles, & the rest coke

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 Fluid Bed Coking & Flexicoking

• Fluid Coking & Flexicoking are expensive processes that have only
a small portion of the coking market
• Continuous fluidized bed technology
» Coke particles used as the continuous particulate phase with a
reactor and burner
• Exxon Research and Engineering licensor of Flexicoking process
» Third gasifier vessel converts excess coke to low Btu fuel gas

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 Fluid Bed Coking — Coke Recycled to
Extinction

Figure from http://www.exxonmobil.com/refiningtechnologies/fuels/mn_fluid.html

51
 Flexicoking

Figure from http://www.exxonmobil.com/refiningtechnologies/fuels/mn_fluid.html

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