Introduction to Refinery operation Overview Of Crude Distillation Delayed Coking History OF Delayed Coking Overview of DCU Process description

Operating modes Chemistry of Delayed coking Process variables

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Following Units Come Under Refinery Operation:

Unit:

Date Commissioned

CDU-I
DCU-I
CCU CDU-II DCU-II

6th Feb 1979

21st Sept 1981
29th Dec 1981 May 1995 May 1996

Delayed Coking
It is a Thermal conversion process where Heavy residue from CDU or/else VDU bottoms are upgraded to more usable hydrocarbon products, such as Gas, LPG, Kerosene, Gas oil and Coke.

History Of Delayed Coking

Pet coke first made in 1860s in Pennsylvania. Only one still was used. Lighter components evaporated Coke was scrapped out. Cokers with horizontal stills and distillation column and tube furnace developed after 1920s Decoking was still the crude manual process First vertical delayed coker was built in 1929 by Standard Oil Company. The concept of recycle was developed subsequently Hydraulic cutting system was first patented by Shell oil in 1930.

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Development of Coking

Cokers became popular after 2nd world war. >> use in Diesel engine locomotives >> Use of gasoline in planes >> development in automobile industry.
Catalytic processes developed during this period had problem of catalyst poisoning. Cokers helped removal of asphaltic content along with metals.

From 1950 to 1970 coking capacity increased 5 folds

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Renewal of Interest
Worldwide crudes are becoming heavier, containing more bottom residues, high CCR, metals, etc. Increasing thrust on residue upgradation - Zero residue refinery

Higher operating/capital cost of other residue upgradation technologies Ability of Delayed Cokers to convert even heaviest residues to lighter distillates - Permits refiners to process wide variety of crudes, dispose low value byproducts Improved profitability through integration with other secondary conversion units

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Process Description

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DCU Configuration - Bongaigaon Refinery

Duel fired Box type natural draft Furnace

Two coke drums One Quench column Fractionator Light end recovery section Vapor blow down system

Safety Blow Down system

Coke cutting and Coke handling system W ater reuse system W ilson Snider 4 - way switching valve

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DCU Configuration - Bongaigaon Refinery

Design Throughput : 1562 tons/Day : 500000 T/year

Maxi design sec. flow to furnace:40m3/pass

Number of on stream days 320 per year

Decoking days : 45 per year

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Process Description

Continuous operation

Feed circuit till the feed furnace

Fractionator along with product strippers & associated equipment

Batch operation Coke drum Cycle time

Coke drum feeding time duration Typical cycle time 24 hrs.
Diagram
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Process Description

Coker Cycle
Chamber Changeover Depressurisation Steam Cooling Low rage water Deluge cooling Draining Deheading Drilling / Decoking Heading Pressure testing Vapor heating/ changeover Idle time : 0 hrs : 0.25hrs : 2hrs : 3hrs : 2hrs : 1.5 hrs : 2 hrs : 6 hrs : 2 hrs :1 hr : 5 hrs : 8hrs

Diagram

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Process Description

Decoking Operation
- Carried by high pressure water jet
- J et pump with a Discharge pressure of 164kg/cm sq. - Coke handling equipment : Galick Crane - W ater reuse/ recirculation system

Diagram

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Operating modes

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Process Description

Operating Characteristics
Two Modes
Needle coke mode Pet coke mode

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Pet Coke mode (feed Characteristics)

Feed:Assam Crude Atm Residue (data IIP and R&D Faridabad) W t % on crude : 40% Sp Gravity : 0.9802 CCR : 5.99 - 6.8 wt% Asphaltene : 1.81- 2.1 wt% Aromatics : 51.6 wt% Saturates : 48.4 wt % W ax 43.4 : 43.4(24.5) wt% Pour point : +48 OC Sulphur : 0.49 wt % Metals V : 0.24 Ni : 1.78 Fe: 14.4 Zn : 0.94 BGR - IOCL Cu : 0.13

Pet Coke mode (feed Characteristics)

Feed:Ravva Crude Atm Residue( Data Cairn Energy and R& D Faridabad) W t % on crude : 33% CCR : 3.1 wt% Asphaltene : 0.8wt% Aromatics : 25.5wt% Saturates : 74.5 wt% W ax Content : 47 % Sulphur : 0.08 wt % Metals : V : 1ppm Na : 16ppm Ni : 1ppm Fe: 1ppm Cu :<1ppm

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Pet Coke mode (feed Characteristics)

Additional feed types

Slop from unit RFO and CFO recycle

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Pet Coke mode (Critical Operating Parameter)

Furnace - COT - BFW

: 496-499 oC : 0.4 m3 /hr/pass for secondary flow of 40m3 /hr/pass or 1vol% - Recycle ratio : 0.8-0.9

Coke Chamber - After quench Temperature 438 440 oC - Bottom Temperature 490-495 OC - Top Pressure 2.1-2.3 kg/cm2g - Bottom Pressure 4.5 5 kg/cm2g
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Pet Coke mode (Critical Operating Parameter)

Quench Column - Top Temperature 430-435 oC Fractionator - Top Pressure 1.50 1.55 kg/cm2g - Top Temperature 102-105OC - Bottom Temperature 360-370 OC

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Pet Coke mode (Product pattern)

PRODU CT S

DE S IG N (W T %)
12.3 7.5 43.0 24.2

ACT U AL (W T % )
7.6 6.8 43.1 29.0

Gas + LPG Coker Naphtha Coker Kero + CGO CFO + RFO

Coke + Loss

13.0

13.5

NB : Design fig is as per Assam crude RCO & Actual yield is as per mixed (Assam + Ravva) crude RCO.
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Product Blending

Coker Naphtha Coker Kero LGO HGO

MS Pool HSD

LDO

CFO
RFO LSHS

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Needle Coke Mode

Used in the manufacture of Graphite electrode. Must have low Low Coefficient of thermal expansion (CTE) i.e expansion between 0 oC and 50 oC Must be able to withstand a temperature of 2800 oC.

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Needle Coke Mode

Feed Characteristics
Should have low Asphaltene content (below 1wt%) Should be aromatic Should have low sulphur content

Feeds used in DCU - RFO (DCU Product) - CFO (DCU Product) - CLO ( Bottom product of FCCU) FBP 550 oC

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Needle Coke Mode

Operating parameters

Furnace

COT BF W Recycle ratio

: 502-504 oC : 0.3m3 /Pass : 1.2-1.3

Chamber
- After quench Temperature 442 oC - Bottom Temperature 495 - 498 OC - Top Pressure 2.7-3 kg/cm2g - Bottom Pressure 5 - 5.5 kg/cm2g

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Needle Coke Mode

Operating parameters

Quench Column - Top Temperature 435-438 oC Fractionator - Top Pressure 2.1 2.3 kg/cm2g - Top Temperature 110-112OC - Bottom Temperature 370 - 372 OC

Cycle time : 30-36 hrs

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PARTICULARS Production of Needle Coke Green Needle Coke Calcined Needle Coke Single Calcined Double Calcined Total CNC CTE Value * 106 IOC (R & D) MS HEG M/S GIL NCFS Prepared Feed Processed Feedstock comp RCO CFO RFO CLO BGR Total - IOCL

1st

2nd

3rd

4th

1290.4
887 887 1.41 8200 8167

981
414 414 1.41 8400 5836

734
605 605 1.1 1.23, 1.22 1.2 8100 6056

665.73
402.55 149 551.55 1.035 1.08 1.22 4000 3631

15% 85% 100%

15% 85% 100%

10% 10% 80% 100%

10% 70% 20% 100%

PARTICULARS Production of Needle Coke Green Needle Coke Calcined Needle Coke Single Calcined Double Calcined Total CNC CTE Value * 106 IOC (R & D) MS HEG M/S GIL NCFS Prepared Feed Processed Feedstock comp RCO CFO RFO CLO Total
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5th
1291

6th
sold to M/S GIL 2059.8

7th
2153.1

8th
1966

9th
2018 (322.59+1639.5) 1962.09 1962.09 1.25/ 1.39 1.42 1.323 10300 9600

1175.7 1175.7
1.22 1.26 1.33 8631 7331

1222.50 1222.50
1.194

1655.6 1655.6
1.31 1.34 12933 12680

1413 1413
1.25 1.30 1.31 13562 12716

11994 11611

5% 14% 81% 100%

13% 83% 5% 100%

14% 83% 3% 100%

16% 82% 2% 100%

100% 100%

1st Parameters Unit

R u n

2nd R u n

3rd

R u n

4th

R u n

5th

R u n

6th

R u n

7th

R u n

8th

r u n

Export Requireme nt 2.14 - 2.15 (0.075 mm) 0.38 - 0.46 0.03-0.10 0.97 - 0.82 (-6.7+ 3.35) 1.0-1.5 0.02 - 0.10 40-50 (3.35 mm), 28-35 (1mm)

Bulk density - 4/6

gm/100cc

82.00 0

79.00 0

82

82

77

79

Real density Sulphur VMC Ash VBD ( - 8/14) PD CTE (0 TO 50 0C) CTE (25 TO 600 0C) Sizing + 6 mesh Moisture Mercurial Density HGI

gm/cc %wt % wt % wt gm/cc gm/cc mm/mm/ 0C*10-7 mm/mm/ 0C*10-6 % % gm/cc

2.130 0.540 0.160 0.100 0.970 *** 1.410 48

2.130 0.540 0.160 0.100 0.970 1.410 48

2.160 0.350 0.060 0.300 1.100 39

2.160 0.500 0.310 0.200 1.035 43

2.15 0.48 0.29 0.28 0.78 1.22 39

2.12 0.45 0.18 0.3 1.194 41

2.15 0.41 0.15 0.15 1.31 37

2.14 0.39 0.15 0.14 1.25 35

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Coking Chemistry

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Crude oil Composition

Courtesy : The Chemistry and Technology of petroleum 2nd Ed

Paraffins
Benzene ring Compounds

Polycondensed
Aromatic Rings

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Coking Chemistry
Feedstock can be divided into asphaltenes and maltenes. Alphaltenes are n-heptane insolubles and maltenes are n-heptane solubles. Maltenes include resins, aromatics and saturates. Asphaltenes are high molecular weight polynuclear aromatics having low H-C ratio Resins are low molecular wt asphaltenes Saturates include Naphthenes, Paraffins. Higher the asphaltenes higher is the coke make.

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Coking Chemistry
o o Free radical Chain reaction Thermal decomposition of hydrocarbon molecules to two free radical fragments. RCH2CH2CH2R -> RCH2H2 + RH2 Free radicals are reactive species which takes the reactions forward in a reaction mass. The reactions that follow are :Combination reactions Disintegration reactions

o o

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Coking Chemistry

Nature of reactions

n-paraffins combine to form larger molecules before decomposition i-paraffins normally produce more olefins Dealkylation of alkylated aromatics or alkylated naphthenes takes place between 350 to 500 OC.

Aromatic ring destruction takes place above 500oC

Condensed ring aromatics decompose at around 450OC.
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Coking Chemistry

Formation of coke
Coke is formed by formation of Thermally stable Pol y nuclear Aromatics(P N A). P N A form by p recipitation by v irt u e of its insol u bilit y in the mother solv ent. The relative aromaticit y or p araffinicit y of the feed effects the sol u bilit y w hich effects the rate of p reci p itation. The q u alit y of the feedstock decides the final sha p e and com p osition of the final coke. H ence, for formation of hi g h q u alit y needle coke feedstock q u alit y is ver y important factor.

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Coking Chemistry

Coke build up in Chamber

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Process Variables

Process Variables

Feed quality Composition & CCR

Operating Pressure Cycle Time Coking Temperature Recycle Ratio

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Process Variables

100
PRODUCT YIELD, Wt%

80 60 40 20 0 0
COKE GAS

10
GASOLINE

20
FEED CCR, Wt%

30
GAS OIL C5 +

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Process Variables
Temperature

Gas
Distillate Coke

Drum pressure Coke Gas

Distillate

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Process Variables

Recycle

Coke ( w t % ) N a p htha H ea v y Gas oil

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Process Variables

Cycle Time
Coke drums have restrictions in max size Coke drum size bottleneck in increasing plant tput. Multiple (<2) coker drums provides higher tput but more slop and loss Shorter cycle time allows higher tput to be processed

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Thank Y ou

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