06 Delayed Coking PDF

Delayed Coking
Chapter 5
Updated: January 26, 2016

Copyright © 2016 John Jechura ([email protected])
Gases
Polymer- Sulfur
ization Plant
Sulfur
LPG
Sat Gas
Gas Plant
Butanes Fuel Gas

Alkyl
Feed LPG
Alkylation
Gas Polymerization
Separation & Naphtha
Stabilizer Isom-
erization
Light Naphtha
Alkylate
Aviation
Isomerate
Gasoline
Automotive
Gasoline
Reformate
Naphtha Solvents
Heavy Naphtha
Hydro-
Naphtha Reforming
treating Naphtha
Atmospheric
Distillation
Jet Fuels
Kerosene
Crude
Desalter Kerosene
Oil
Distillate Cat Solvents
AGO Hydro-
Naphtha Distillate
cracking Treating &
Hydro-
Blending
Heating Oils
treating
Gas Oil Fluidized
Cat Diesel
LVGO Hydro- Catalytic
treating Cracking Distillates
Vacuum
Distillation
Fuel Oil
HVGO
Cycle Oils
Residual
Fuel Oils
DAO
Solvent
Deasphalting SDA
Coker Asphalts
Bottoms
Naphtha Naphtha
Visbreaking Heavy Distillates

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

Copyright © 2016 John Jechura ([email protected]) 2
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/

3
U.S. Refinery Implementation
EIA, Jan. 1, 2015 database, published June 2015

http://www.eia.gov/petroleum/refinerycapacity/

4
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
“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

6
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

7
Coking Chemistry
• “Carbon rejection” process • Conditions
 Coke has very little hydrogen – contained in lighter  High temperatures & low pressures favor cracking
products
• More distillate liquids
 Metals (catalyst poisons) concentrate in coke • Lower yields of coke & hydrocarbon gas
• Cycle of cracking & combining  High residence time favor the combining reactions
 Side chains cracked off of PNA (Polynuclear  Over conversion will reduce distillates & produce
Aromatic) cores coke and hydrocarbon gases
• 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
Figure: “Comparison of thermal cracking and hydrocracking yield distributions,” Sayles & Romero
http://www.digitalrefining.com/article_1000070.pdf

8
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

9
Solid Products
• Coke with large amounts of metals & • Fuel grade coke
sulfur may pose a disposal problem
 Feedstock – resid high in polynuclear aromatics &
 Oil sands pile it up sulfur
• Product grades  Value similar to coal
 Needle coke • High quality products
 Anode grade  Needle coke
 Fuel grade • Feedstock – FCC cycle oils & gas oils
• Product Morphology • Used for electrodes in steel manufacturing

• 10X or more value of fuel-grade coke
 Needle coke
• Hydroprocessing upstream of delayed coker may
 Sponge coke be used to make high quality coke
 Shot coke  Anode grade coke
• Feedstock – resids with small ring aromatics, low
metals, & low sulfur
• Used for anodes in aluminum production

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

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
• Hydrocracker—processes 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

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 )

13
Example Yield Problem
Coker Calculations
CCR Sulfur Nickel Vanadium Yield Yield
bbl/day lb/day SpGr lb/gal °API wt% wt% ppm ppm wt% vol%
Vac Resid Feed 40,000 14,056,164 1.0035 8.367 9.5 13.5 2.85 65 145
Coker Gas 1,369,633 8.77 9.74
Coker Gasoline 8,423 2,237,812 0.7587 6.326 55.0 0.90 15.92 21.06
Coker Gas Oil 23,263 7,412,589 0.9100 7.587 24.0 1.89 52.74 58.16
Coke 3,036,132 3.96 301 671 21.60
Coker Total 14,056,164 100.00
Sulfur Distribution Coker Gas Composition

Sulfur (%) lb/day mol/day Corrected Corrected Corrected
Gas 30.0 120,180 3,748 Component Mol% Mol Wt mol/day mol/day Mol% lb/day
Light Naphtha 1.7 6,810 Methane 51.4 16.043 28,966 28,966 51.4 464,694
Heavy Naphtha 3.3 13,220 Ethene 1.5 28.054 845 845 1.5 23,714
LCGO 15.4 61,693 Ethane 15.9 30.070 8,960 8,960 15.9 269,433
HCGO 19.6 78,518 Propene 3.1 42.081 1,747 1,747 3.1 73,514
Coke 30.0 120,180 Propane 8.2 44.097 4,621 4,621 8.2 203,771
Total 100.0 400,601 Butenes 2.4 56.108 1,352 1,352 2.4 75,885
I-Butane 1.0 58.123 564 564 1.0 32,755
N-Butane 2.6 58.123 1,465 1,465 2.6 85,163
H2 13.7 2.016 7,720 3,972 7.0 8,008
CO2 0.2 44.010 113 113 0.2 4,960
H2S 34.080 3,748 6.7 127,736
Sulfur 32.064 3,748
Total 100.0 60,102 56,354 100.0 1,369,633
Example steps w/o Sulfur 22.171 56,354 1,249,452
Corrected in units of MMscf/day 21.39

14
Boiling Point Ranges for Products
Kaes's Example Coker Problem
1,000
42-hcgo
900 53+55
40-lcgo
800 37-unstab
33-wetgas
lab-vac-resid
700
Incremental Yield [bpd]
600
500
400
300
200
100
-
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
BPT [°F]

15
Configuration
• Typical equipment
 Heater (furnace) & Preheat train Gas
 Coke drum vessels

Naphtha
 Fractionator
 Downstream vapor processing
Coke Drums
vessels Light Gas Oil
Heavy Gas Oil
• Coke drums run in two batch

modes
Fractionator
Coke
 Filling
 Decoking Fired Heater
Steam
• Both modes of operation Fresh Feed
concurrently feed to the

fractionator

Delayed Coker

17
Typical Delayed Coking Unit
Original Source:
“An Oil Refinery Walk-Through”,
by Tim Olsen, Chemical Engineering Progress, May 2014

18
Original Source:
Refining Overview – Petroleum Processes & Products,
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD-ROM, 2000

19
• Fresh Feed & Furnace • Coke Drum Configuration
 Fresh feed to bottom of fractionator  Flow up from bottom
 Total feed (fresh feed + recycle) heated  Coking reaction are completed in drum
in furnace
 Vapors out top of drum to fractionator
• Furnace  Even number of coke drums
 Outlet temperature about 925°F • Typically two or four
• Cracking starts about 800°F • Operate as pairs, one filling while the
 Endothermic reactions other decoked
 Superheat allows cracking reactions to • Fractionator

continue in coke drums– “Delayed  Vapors compressed & sent to gas plant
Coking”
 Naphtha condensed from fractionator
 Steam injected into furnace overhead
• Reduce oil partial pressure & increase
 Gas oils are side stream draws from
vaporization
fractionator
• Maintains high fluid velocities
 Flash Zone Gas internally recycled to
coke drums or recovered as additional
liquid
20
• Coke Drum Cyclic Operation
 Fill Coke Drum  Coke Collection Systems
• Coking reaction in drums & solid • Direct discharge to hopper car
coke deposited
• Pad loading
• Gas from top of coke drum to
• Pit & crane loading
fractionator
• 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
“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

22
Coke Drum Schedule – 1 Pair
Drum Being Filled Drum Being Decoked Fractionator

1 hour - Steam out (to Fractionator)
4 hours - Quench (to closed blowdown 4 - 5 hours - Upset from switchover

system)
1.5 hours - Dehead
16 hours - Fill drum with coke

4 hours - Drill out coke
11 hours - Lined out & steady

1 hour - Rehead
4.5 hours – Test, Warmup, & Standby

23
Coke Drum Schedule – 3 Pairs
Handbook of Petroleum Refining Processes

Robert Meyers
McGraw-Hill, Inc, 1986

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

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

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

27
Decoking
Decoking to rail car Decoking to pit

Robert Meyers

28
Coke Products
• Green Coke Calcined
Green Coke
 Directly produced by a refinery Coke
if no further processing done
Fixed carbon 86% - 92% 99.5%
 Primarily used for fuel
• Uncalcined sponge coke Moisture 6% - 14% 0.1%
typically 14,000 Btu/lb
heating value Volatile matter 8% - 14% 0.5%
• Crushed & drained of free
water Sulfur 1% - 6% 1% - 6%
• Calcined Coke Ash 0.25% 0.40%
 Green coke heated to finish Silicon 0.02% 0.02%

carbonizing coke & reduce Nickel 0.02% 0.03%
volatile matter to very low
levels Vanadium 0.02% 0.03%
 Anode & needle coke 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

Robert Meyers

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
Fluid Bed Coking Flexicoking
Figures from http://www.exxonmobil.com/refiningtechnologies/fuels/mn_fluid.html

31
Supplemental Slides
• Delayed coker installed cost
• Coking technology providers

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

33
Coking Technologies
Provider Features
Bechtel
Delayed Coking with unique features of: furnace design;
KBR
coke drum structure, design, layout, & scheduling; coke
Lummus Technology
handling
UOP / Foster Wheeler
ExxonMobil Fluidized bed

34

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Delayed Coking

Updated: January 26, 2016

Butanes Fuel Gas

Visbreaking Heavy Distillates

Updated: January 26, 2016

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

Updated: January 26, 2016

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

Updated: January 26, 2016

Updated: January 26, 2016

Updated: January 26, 2016

Updated: January 26, 2016

Updated: January 26, 2016

Updated: January 26, 2016

• Product Morphology • Used for electrodes in steel manufacturing

Updated: January 26, 2016

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

Updated: January 26, 2016

Updated: January 26, 2016

Updated: January 26, 2016

Sulfur Distribution Coker Gas Composition

Updated: January 26, 2016

Updated: January 26, 2016

 Coke drum vessels

Heavy Gas Oil

• Coke drums run in two batch

• Both modes of operation Fresh Feed

concurrently feed to the

Updated: January 26, 2016

Updated: January 26, 2016

Updated: January 26, 2016

Updated: January 26, 2016

 Superheat allows cracking reactions to • Fractionator

Updated: January 26, 2016

Updated: January 26, 2016

Drum Being Filled Drum Being Decoked Fractionator

4 hours - Quench (to closed blowdown 4 - 5 hours - Upset from switchover

1.5 hours - Dehead

16 hours - Fill drum with coke

11 hours - Lined out & steady

4.5 hours – Test, Warmup, & Standby

Updated: January 26, 2016

Handbook of Petroleum Refining Processes

Updated: January 26, 2016

 Remotely operated from control room

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

Updated: January 26, 2016

Updated: January 26, 2016

Updated: January 26, 2016

Decoking to rail car Decoking to pit

Handbook of Petroleum Refining Processes

Updated: January 26, 2016

• Calcined Coke Ash 0.25% 0.40%

 Green coke heated to finish Silicon 0.02% 0.02%

 Anode & needle coke Iron 0.01% 0.02%

Updated: January 26, 2016

Handbook of Petroleum Refining Processes

Updated: January 26, 2016

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