Delayed Coking

Chapter 5

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

Gases
Sulfur
Plant

Polymerization
Sat Gas
Plant

Gas

LPG

Alkylation

Polymerization
Naphtha

Isomerization

Light Naphtha

Fuel Gas

Butanes

Alkyl
Feed
Gas
Separation &
Stabilizer

Alkylate

Isomerate

Aviation
Gasoline
Automotive
Gasoline

Reformate
Naphtha
Hydrotreating

Heavy
Naphtha

Sulfur

LPG

Naphtha
Reforming

Solvents

Naphtha

Atmospheric
Distillation

Crude
Oil

Jet Fuels

Kerosene

Desalter

Distillate

Hydrocracking

AGO

LVGO
Vacuum
Distillation

Kerosene

Gas Oil
Hydrotreating

Fluidized
Catalytic
Cracking

Cat
Naphtha

Cat
Distillates

Solvents
Distillate
Hydrotreating

Treating &
Blending

Heating Oils
Diesel

Fuel Oil

HVGO

Cycle Oils

Residual
Fuel Oils

DAO
Solvent
Deasphalting

Visbreaking

Vacuum
Residuum

Coker
Naphtha

Heavy
Coker
Gas
Oil

SDA
Bottoms

Asphalts

Naphtha

Distillates
Fuel Oil
Bottoms
Lube Oil

Lubricant
Greases

Solvent
Dewaxing

Waxes
Waxes

Coking

Light Coker
Gas Oil

Coke

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

U.S. Refinery Implementation

Coking capacity

reported in terms of
both coke production in
tons per day & residual
oil feed rate in barrels
per day

EIA, Jan. 1, 2015 database, published June 2015

http://www.eia.gov/petroleum/refinerycapacity/
Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

U.S. Refinery Implementation

EIA, Jan. 1, 2015 database, published June 2015

http://www.eia.gov/petroleum/refinerycapacity/
Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

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

Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

Improve coker efficiency with reliable valve automation

B. Deters & R. Wolkart, Hydrocarbon Processing, April 2013

Characteristics of Petroleum Products

Conversion to light products w/o extra hydrogen requires significant coke formation
Refining Overview Petroleum Processes & Products,
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD-ROM, 2000

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

Coking History
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

Delayed coking
Predominate coking technology
Delayed Coking technology is relatively inexpensive
Open art available
Companies do license technology emphasizing coke furnaces, special processing modes, &
operations

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

Coking Chemistry
Carbon rejection process

Conditions

Coke has very little hydrogen contained in lighter

products
Metals (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

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

PNAs combine (condense) to form asphaltenes &

coke
Metals & heteroatoms in PNA cores end up in coke

Figure: Comparison of thermal cracking and hydrocracking yield distributions, Sayles & Romero
http://www.digitalrefining.com/article_1000070.pdf
Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

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% or more

Feed ultimately depends on type of coke desired

Specialty cokes require careful choice of crude oil feedstocks
Using feedstocks other than vac resid may lessen this requirement

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

Solid Products
Coke with large amounts of metals &
sulfur may pose a disposal problem
Oil sands pile it up

Product grades
Needle coke
Anode grade
Fuel grade

Product Morphology
Needle coke
Sponge coke
Shot coke

Fuel grade coke

Feedstock resid high in polynuclear aromatics &
sulfur
Value similar to coal

High quality products

Needle coke
Feedstock FCC cycle oils & gas oils
Used for electrodes in steel manufacturing
10X or more value of fuel-grade coke
Hydroprocessing upstream of delayed coker may
be used to make high quality coke

Anode grade coke

Feedstock resids with small ring aromatics, low
metals, & low sulfur
Used for anodes in aluminum production

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

10

Solid Products
Morphology
Needle coke
Very dense & crystalline in structure

Sponge coke
Is sponge-like in structure

Shot coke
Cannot avoid based on asphaltene content
of feed
From size of small ball bearings to basketball
Operational adjustments required in cutting
& handling of coke

Managing Shot Coke: Design & Operation, John D. Elliott

http://www.fwc.com/getmedia/5fec2c99-879e-4bbc-a296-77971b85df89/ManagingShotCoke-Design-OperationA-4Rev1.pdf.aspx?ext=.pdf
Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

11

Light Products
Vapor light ends processed in refinery gas plant
Liquids
Naphtha fraction
May be used as catalytic reformer feed after hydrotreating
Small fraction of gasoline pool

Light Gas Oil

Used in diesel pool after hydrotreating
Hydrocrackerprocesses aromatic rings

Heavy Gas Oil fed to catalytic cracker or hydrocracker (preferred)

Flash Zone Gas Oil
Increases liquid yield & reduces coke make

Composition
Some of the lowest quality in the refinery
Reduced aromatics but high olefin content
Though heteroatoms are concentrated in coke still high in sulfur

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

12

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 )

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

13

Example Yield Problem

Coker Calculations

Vac Resid Feed

Coker Gas
Coker Gasoline
Coker Gas Oil
Coke
Coker Total

bbl/day
40,000
8,423
23,263

lb/day
14,056,164
1,369,633
2,237,812
7,412,589
3,036,132
14,056,164

SpGr
1.0035

lb/gal
8.367

0.7587
0.9100

6.326
7.587

Sulfur Distribution

API
9.5

CCR
wt%
13.5

Sulfur
wt%
2.85
8.77
0.90
1.89
3.96

55.0
24.0

Nickel
ppm

Vanadium
ppm
65
145

301

671

Yield
wt%
9.74
15.92
52.74
21.60
100.00

Yield
vol%

21.06
58.16

Coker Gas Composition

Sulfur (%)
Gas
30.0
Light Naphtha
1.7
Heavy Naphtha
3.3
LCGO
15.4
HCGO
19.6
Coke
30.0
Total
100.0

lb/day
120,180
6,810
13,220
61,693
78,518
120,180
400,601

mol/day
3,748

Example steps
Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

Component
Methane
Ethene
Ethane
Propene
Propane
Butenes
I-Butane
N-Butane
H2
CO2
H2S
Sulfur
Total
w/o Sulfur

Mol%
Mol Wt
mol/day
51.4
16.043
28,966
845
1.5
28.054
15.9
30.070
8,960
3.1
42.081
1,747
8.2
44.097
4,621
2.4
56.108
1,352
1.0
58.123
564
2.6
58.123
1,465
13.7
2.016
7,720
0.2
44.010
113
34.080
32.064
3,748
100.0
60,102
22.171
56,354
Corrected in units of MMscf/day

Corrected Corrected Corrected

mol/day
Mol%
lb/day
464,694
28,966
51.4
1.5
845
23,714
8,960
15.9
269,433
1,747
3.1
73,514
4,621
8.2
203,771
1,352
2.4
75,885
564
1.0
32,755
1,465
2.6
85,163
3,972
7.0
8,008
113
0.2
4,960
3,748
6.7
127,736
56,354

100.0

1,369,633
1,249,452

21.39

14

Boiling Point Ranges for Products

Kaes's Example Coker Problem
1,000

Incremental Yield [bpd]

42-hcgo
900

53+55

800

37-unstab

40-lcgo
33-wetgas
lab-vac-resid

700
600
500
400
300
200
100
0

100

200

300

400

500

600

700

800

900 1000 1100 1200 1300 1400 1500

BPT [F]

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

15

Configuration
Typical equipment
Heater (furnace) & Preheat train

Gas

Coke drum vessels

Naphtha

Fractionator
Downstream vapor processing
vessels

Coke Drums
Light Gas Oil
Heavy Gas Oil

Coke drums run in two batch

modes

Coke

Filling
Decoking

Both modes of operation

Fractionator

Fired Heater
Steam
Fresh Feed

concurrently feed to the

fractionator

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

16

Delayed Coker

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

17

Typical Delayed Coking Unit

Original Source:
An Oil Refinery Walk-Through,
by Tim Olsen, Chemical Engineering Progress, May 2014
Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

18

Typical Delayed Coking Unit

Original Source:
Refining Overview Petroleum Processes & Products,
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD-ROM, 2000
Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

19

Typical Delayed Coking Unit

Fresh Feed & Furnace

Coke Drum Configuration

Fresh feed to bottom of fractionator

Flow up from bottom

Total feed (fresh feed + recycle) heated

in furnace

Coking reaction are completed in drum

Furnace
Outlet temperature about 925F
Cracking starts about 800F

Endothermic reactions
Superheat allows cracking reactions to
continue in coke drums Delayed
Coking
Steam injected into furnace
Reduce oil partial pressure & increase
vaporization
Maintains high fluid velocities

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

Vapors out top of drum to fractionator

Even number of coke drums
Typically two or four
Operate as pairs, one filling while the
other decoked

Fractionator
Vapors compressed & sent to gas plant
Naphtha condensed from fractionator
overhead
Gas oils are side stream draws from
fractionator
Flash Zone Gas internally recycled to
coke drums or recovered as additional
liquid
20

Typical Delayed Coking Unit

Coke Drum Cyclic Operation
Fill Coke Drum
Coking reaction in drums & solid
coke deposited
Gas from top of coke drum to
fractionator

Coke Collection Systems

Direct discharge to hopper car
Pad loading
Pit & crane loading

Full cycle time till coke drum full

Decoking
Off-line drum decoked
Quench step hot coke quenched
with steam then water. Gives off
steam & volatile hydrocarbons
Initial steam purge fed to
fractionator. Further purge directed
to blowdown system.
Coke drilled out with water drills

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

Improve coker efficiency with reliable valve automation

B. Deters & R. Wolkart, Hydrocarbon Processing, April 2013

21

Filling of Coke Drums

http://www.glcarbon.com/ref/delayed.PDF
Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

22

Coke Drum Schedule 1 Pair

Drum Being Filled

Drum Being Decoked

1 hour - Steam out (to Fractionator)

Fractionator

4 hours - Quench (to closed blowdown

system)

4 - 5 hours - Upset from switchover

1.5 hours - Dehead

16 hours - Fill drum with coke

4 hours - Drill out coke

1 hour - Rehead

11 hours - Lined out & steady

4.5 hours Test, Warmup, & Standby

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

23

Coke Drum Schedule 3 Pairs

Handbook of Petroleum Refining Processes

Robert Meyers
McGraw-Hill, Inc, 1986
Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

24

Deheading
Transitioning from manual to automatic
deheading

Totally enclosed system from the top of

coke drum to the drain pit, rail car, or
sluice way
Eliminate exposure risk to personnel,
equipment, & the unheading deck

http://www.processengr.com/ppt_presentations/coking_101.pdf

Remotely operated from control room

All safety interlocks incorporated
Isolation & control of a drum dump

Managing Shot Coke: Design & Operation, John D. Elliott

http://www.fwc.com/getmedia/5fec2c99-879e-4bbc-a296-77971b85df89/ManagingShotCoke-Design-OperationA-4Rev1.pdf.aspx?ext=.pdf
Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

25

Side Feed with Automatic Deheading

Automatic deheading
requires feed entry
from the side

Without special

injection port get

swirling entry instead
of flow pattern straight
up

http://deltavalve.cwfc.com/products/PDFs/DeltaValveRetractableCenterFeedInjectionDevice.pdf
Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

26

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 direction predominantly top to
bottom
Bottom up cutting risks stuck drill if bed
collapses

The coke falls from coke drum into a

collection system
Automated decoking solves coker safety challenges
I. Botros, Hydrocarbon Processing, pp 47-50, November 2011

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

27

Decoking

Decoking to rail car

Decoking to pit

Handbook of Petroleum Refining Processes

Robert Meyers
McGraw-Hill, Inc, 1986

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

28

Coke Products
Green Coke
Directly produced by a refinery
if no further processing done
Primarily used for fuel
Uncalcined sponge coke
typically 14,000 Btu/lb
heating value
Crushed & drained of free
water

Calcined Coke
Green coke heated to finish
carbonizing coke & reduce
volatile matter to very low
levels
Anode & needle coke

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

Green Coke

Calcined
Coke

Fixed carbon

86% - 92%

99.5%

Moisture

6% - 14%

0.1%

Volatile matter

8% - 14%

0.5%

Sulfur

1% - 6%

1% - 6%

Ash

0.25%

0.40%

Silicon

0.02%

0.02%

Nickel

0.02%

0.03%

Vanadium

0.02%

0.03%

Iron

0.01%

0.02%

29

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 2400oF
Calcining does not remove
metals

Handbook of Petroleum Refining Processes

Robert Meyers
McGraw-Hill, Inc, 1986

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

30

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
Flexicoking

Fluid Bed Coking

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

Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

31

Supplemental Slides
Delayed coker installed cost
Coking technology providers

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

32

Delayed Coker Installed Cost

Includes
Coker fractionator
Hydraulic decoking equipment
Coke dewatering, crushing, & separation
3 days covered coke storage
Coke drums 50 60 psig
Blowdown condensation & wastewater
purification
Liquid product heat exchange to ambient
temperature

Excludes
Light ends facilities
Light ends sulfur removal
Product sweetening
Cooling water, steam & power supply
Off gas compression
Petroleum Refining Technology & Economics, 5th ed.
Gary, Handwerk, & Kaiser
CRC Press, 2007
Updated: January 26, 2016
Copyright 2016 John Jechura (jjechura@mines.edu)

33

Coking Technologies
Provider
Bechtel
KBR
Lummus Technology
UOP / Foster Wheeler
ExxonMobil

Features
Delayed Coking with unique features of: furnace design;
coke drum structure, design, layout, & scheduling; coke
handling
Fluidized bed

Updated: January 26, 2016

Copyright 2016 John Jechura (jjechura@mines.edu)

34