Presentation On Delayed Coking Technology

BIRENDRA KUMAR (CTSM) BARAUNI REFINERY

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PRESENTATION ON DELAYED COKER

Topics of Discussion
Thermal

Cracking

Brief Overview of Delayed Coker Feedstock Operating variables Coking reactions Products Coke formation and type of coke. Coke Drum Cycle Safety Hazards Modern Delayed Coker Design Features

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Thermal Cracking Process

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PRESENTATION ON DELAYED COKER Requirement of Thermal Cracking

Residual fractions (Bottom of Barrel) are the least valuable streams of a refinery. Nearly 45% - 50% of the typical crude oil processed in Indian Refineries contain 370 C+ fractions. Worldwide limited reserve of sweet crudes. Disposal problems due to stringent environmental norms. Decreasing demand of fuel oil. Gradually increasing demand of middle distillates.

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Advantages of Thermal Cracking

Thermal Cracking It is simple and cost effective process. However, rapid uncontrolled thermal cracking produces undesirable products like gas and coke. Limitations of Catalytic Cracking for Resid Processing In resid feedstock presence of high molecular weight compounds like resins, asphaltenes and metals make it unsuitable for catalytic cracking. RFCC can process resid feed only upto a certain limit. Metals and sulphur compounds present in resid feedstock act as catalyst poison.

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Various Thermal Cracking Processes

VISBREAKING It is a thermal cracking process producing gas, distillates and visbroken residue (FO).

DELAYED COKING Continuous thermal cracking process which generates coke and produces various distillates in fractionator from vacuum residue. Coke drum temperature remains around 415 C 450 C. FLUID COKING Continuous coking process where residuum is sprayed on to fludised bed of hot coke particles. Here cracking takes place at much higher temperature than delayed coking (temperature upto 565 C). FLEXI COKING Continuous coking process like Fluid Coking which includes a gasification section of coke produced in Fluid Coking Operation.

Among the above processes Delayed Coking is most popular.

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Thermal Cracking Reactions
Thermal cracking reactions take place due to application of heat. During the cracking process, large molecules decompose and form smaller (lighter) molecules. In thermal cracking generally two types of reactions take place Primary reactions by decompositions of large molecules to smaller molecules. Secondary reactions by which active products from primary cracking reactions further crack or react to form other molecules or polymerize to generate heavy products (coke).

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Thermal Cracking Reactions
Thermal cracking of long chain oil molecules into shorter chains proceeds through a free radical mechanism CnH2n+2 Cn-2H2n2n-3 + C2H5 with other

Initially formed free radicals readily combine hydrocarbons/free radicals/decomposed to form olefins. C2H5 + CnH2n+2 CnH2n+1 CnH2n+1 Cn-2H2n2n-3 + H Cn-2H2n2n-3 CnH2n+1 + C2H6 Cn-1H2n2n-2 + CH3 CnH2n + H Cn-2H2n2n-2 C(n(n-2)/2Hn-2 + C(n(n-2)/2Hn-1

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PRESENTATION ON DELAYED COKER Thermal Cracking Reactions

Aromatics & polyneuclear aromatics undergo condensation reaction with the formation of Asphaltenic compounds (coke forming compounds). Some typical reactions are

+
CH3 CH3 CH3 CH3

+ H2

+ 2H2

+ H2

+ 2H2

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Delayed Coking Technology

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PRESENTATION ON DELAYED COKER

Delayed Coking is the most commonly used carbon rejection process that upgrades residues to a wide range of lighter hydrocarbon gases and distillates through thermal cracking. The byproduct of delayed coking process is petroleum coke. The goal for delayed coker operation is to maximise the yield of clean distillates and minimise the yield of coke. Delayed coking technology is preferred for upgrading heavier residues due to its inherent flexibility to handle even the heaviest residues while producing clean liquid products. The main products of delayed coker operation is off-gas (from which LPG is recovered), naphtha, Light Gas Oil (LCGO) and Heavy Gas Oil (HCGO). LCGO is sent to Hydrotreater for production of Gas Oil and HCGO to refinery FO Pool/ RFCC feedstock/ OHCU feedstock.

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The yield slate for a Delayed Coker can be varied to meet a refiners objective through the selection of operating parameters. Three operating parameters govern the yield pattern and product quality of Delayed Coker Temperature Pressure Recycle Ratio (RR) Increasing coking temperature decreases coke production and increases liquid yield and gas oil endpoint. However, temperature can be adjusted only a narrow range to control volatilities left in coke. Increasing pressure and/or Recycle Ratio (RR) increases gas and coke make and decreases liquid yield and gas oil endpoint. RR can be varied from 0% to 120%. Recycle Ratio is defined as (Composite feed to Coker Heater)/ (Primary feed to Fractionator bottom)
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PRESENTATION ON DELAYED COKER

Modern trend of Delayed Coking technology is to minimise the coking pressure and recycle ratio within the economic and technical constraints for designing a unit while producing clean Heavy Coker Gas Oil (HCGO) product within following quality Low contaminant level of carbon residue. Low contaminant level of metal. End point within acceptable level. Delayed Coker products typically require further downstream hydroprocessing because of hydrogen deficiency and sulphur contamination. Fuel grade coke is a low value byproduct. However it has significant demand as a clean and economic fuel.

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PRESENTATION ON DELAYED COKER Delayed Coking Feedstock

Delayed Coker can process a wide variety of feedstocks : Feedstock can have considerable amount of metal (Ni + V), Sulphur, Resins and Asphaltenes. Contaminants present in feedstock mostly gets eliminated with coke. Most typical feedstock is Vacuum Residue (530 C +). It can also process refinery slop oil/ sludge. Atmospheric residue is also occasionally processed. Typical feed composition Sulphur 5 to 6 % wt Metals 1000 ppmw. CCR 20 TO 30 % wt. Properties of coke mostly depends on feed quality.
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Delayed Coking Process

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PRESENTATION ON DELAYED COKER Delayed Coking Chemical Reactions

Carbonization is the thermal conversion of organic materials to carbon/ coke.
Carbonization involves a complex series of chemical reactions and diffusion processes in both liquid and solid state. The reaction sequence consists of the elimination of substituent atoms and groups from the organic molecule and subsequent polymerisation to a large aromatic carbon framework. Petroleum coke mainly formed by two different mechanisms High molecular weight compounds, such as asphaltenes and resins, tend to dealkylate to straight chain compounds and CH2 groups when subjected to high temperature. In this process a residue of carbon (i.e coke) is left behind. Dehydrogenation of heavy oils followed by polymerisation and condensation of free radicals from high molecular weight compounds (mainly aromatic hydrocarbon) lead to formation of coke.

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Chemical Reactions of Carbonization

There are three types of chemical reaction processes which occur continuously without any distinct steps in the coking process Dehydrogenation The initial reaction in carbonization involves the loss of hydrogen atom from an aromatic hydrocarbon and formation of aromatic free radical intermediate. Rearrangement Reactions Thermal rearrangement usually leads to formation of more stabilised aromatic ring system which forms building block of graphite growth. Polymerisation of aromatic radicals Aromatic free radicals get polymerised in the process of coking reaction. This process is initiated in the liquid phase and continued in different steps.

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Delayed Coking Process

Delayed Coking is a batch cum continuous process Flow through the furnace coil is continuous. Feed is switched between two or more drums in batchwise fashion. Delayed coker drum cycle length varies from unit to unit. However, typically it is kept within 16 to 24 hours. Adequate time should be given for coke drum cooling / heating to avoid any thermal shock/ degradation of coke drum metallurgy.

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PRESENTATIONONDELAYEDCOKER
410OC 115OC 1.8 kg/cm2g

QUEN CH COLn MAIN 200OC FRACTI ONATOR

405 C
O

OFFGAS
SOUR WATER

NAPHTHA
45OC

420OC

FRESH FEED
45 C
O

LDO / SLOP QUENCH BFW

MP STEAM BFW
95OC

MP STEAM

LCGO - I
MP STEAM
BFW

45OC IR 280OC CR

LCGO - II
BFW MP STEAM

REAC TOR

REAC TOR

BFW

RFO
FLUE GAS
485OC 485OC 240OC 330OC FO IR
MP STEAM

95OC

HCGO
BFW

BFW

FURNACE

340OC

340OC

PETRO COKE
502OC

BOTTOM PUMP

DCU FLOW DIAGRAM

BOTTOM PUMP

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PRESENTATION ON DELAYED COKER

TypicalDrumCycleTime Drum Cycle Steam to Fractionator Steam to Blowdown Low range cooling & water quench Depressurisation & Drain Unheading top and bottom cover Coke Cutting Reheading/ steam testing/ purge Drum warm-up/ Vapour heating Change-over / Drum Switch Total
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Hours 0.5 1.5 4.5 2.0 1.0 3.0 1.0 4.0 0.5 18.0

PRESENTATIONONDELAYEDCOKER
LITTLE STEAM BIG STEAM LITTLE WATER BIG WATER

CYCLIC PROCESS OF DELAYED COKING

WATER DRAIN COKING CYCLE OF A COKE DRUM DECOKING CYCLE OF A COKE DRUM

COKE DRUM UNHEADING COKING COKE DRUM PREHEAT COKE DRUM STEAM PR. TEST COKE DRUM STEAM PURGE Barauni Refinery HYDRAULIC DECOKING COKE DRUM HEADING

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PRESENTATION ON DELAYED COKER

Coke Drum Warm-up To prepare the empty coke drum for receiving feedstock ex process heater, hot vapors from online drum are circulated into the empty drum for preheating of coke drum. The hot vapours (at around 415 C) condenses inside the cold vapour drum, heating the drum to a target temperature of around 340 C. Condenser vapours are continuously drained out of the drum initially through the blowdown circuit and later to main fractionator. After vapour heating the drum for few hours, hot oil (RCO/ VR) ex furnace (at around 485 C) is switched to drum. Most of the vapour condenses on the colder wall of the drum , liquid remaining as boiling pool of oil at the bottom.

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Steam Stripping Steam must be flowing before the switch and immediately after the switch and immediately after the switch otherwise the neat unconverted feedstock on the top of coke bead will run down the channels which will solidify and plug the channels. This will lead to isolation / plugging of the coked portion from steam and cooling water resulting in formation of hot spots. These hot spots may result in dangerous steam eruption during cutting of coke which is a potential safety hazard. Steam stripping also serves to transfer heat from the hot bottom portion of the coke bed to unconverted liquid present at the top of the coke drum. Adequate steam stripping increases the quantity of recovered gas oil as well as reduce the amount of volatile matter present in the bottom section of the coke drum.

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PRESENTATION ON DELAYED COKER

Delayed Coking Products

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PRESENTATION ON DELAYED COKER Products of Delayed Coking

Delayed coker produces desirable liquid products (naphtha and gas oil) and byproducts coker gas and solid coke. Coker off-gas goes to the gas plant where C3 and C4 is recovered as LPG and the lighter end can be used as fuel gas in the refinery. Naphtha ex coker unit contains high olefin content and this stream is usually sent to hydrotreater for stabilisation. Light Coker Gas Oil (LCGO) is sent to diesel hydrotreater for production of diesel. Typical end point of this stream is around 370 C. Heavy Coker Gas Oil (HCGO) is sent to FCC/ RFCC for production of valuable distillate products. Typical end point of this stream is around 538 C.
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PRESENTATION ON DELAYED COKER Typical Yield Pattern of Delayed Coking

PARTICULARS Feed Quality :Feed CCR, % wt Feed S, % wt Yield Pattern (% wt) : Gas + H2S LPG Light Naphtha Heavy Naphtha LCGO HCGO Coke 5.0 3.0 6.0 5.0 32.0 19.0 30.0
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PR 22 4.8

BR 11 1.2 8.0 4.0 8.0 40 15 25

PRESENTATION ON DELAYED COKER

Type of Coke
Coke formed in Delayed Coker Unit can be classified into three different types Sponge Coke Needle Coke Shot Coke

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PRESENTATION ON DELAYED COKER

Sponge Coke
Sponge Coke is porous, irregular shaped lumps. It was named by its sponge like appearance. Vacuum Residue with low to moderate asphaltene produces sponge coke. Most of the sponge coke is used as fuel. Some sponge coke with low sulphur (< 2% wt) and metal content can be used to make anodes used in aluminium industries.

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Needle Coke
It is a premium coke from Delayed Coker named by its needle like appearance. Feedstock with aromatic component (without much asphaltene) helps to produce needle coke. FCCU decant oil after hydrodesulphurisation for removal of sulphur used as needle coke feedstock. It has microscopic, elongated, needle like structure. It has very low coefficient of thermal expansion (CTE) and electrical resistance suitable for using as electrodes in steel making.

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Shot Coke
It is formed from high asphaltene content feedstock present at high coke drum temperature. Shot coke is undesirable product in delayed coking. With the light ends flashing-off small globules of tar are formed which rapidly converted to coke due to huge heat generation during exothermic asphaltene polymerisation reaction. Shot coke is usually blended with sponge coke to use as fuel.

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PRESENTATION ON DELAYED COKER Comparison of Different Types of Coke

Sponge Coke Needle Coke Shot Coke

Porous, irregular Needle like shaped. structure. Feed Moderate Feed Low S, asphaltene level. very low High S Fuel asphaltene with Grade. aromatic Low S Anode component. Grade. Premium Grade Coke. Very low CTE.

Undesirable. Feed High Asphaltene. Difficult and unsafe to handle.

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PRESENTATION ON DELAYED COKER

Thumb Rule for Yield Prediction

Coke and liquid yields can be predicted by simple equationa as under Coke Yield (wt%) = 1.6 X (wt% feed CCR) Gas (C4 - ), wt% = 7.8 + 0.144 X (wt% feed CCR) Gasoline (wt%) = 11.29 + 0.343 X (wt% feed CCR) Gas Oil (wt%) = 100 wt % coke wt % gas wt % Gasoline

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PRESENTATION ON DELAYED COKER

Effect of Operating Variables

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PRESENTATION ON DELAYED COKER Effect Of Coke Drum Temperature

At constant pressure and recycle ratio, the coke yield decreases and distillate yield increases as drum temperature increases. If the temperature is too low, the coking reaction does not proceed far enough and pitch and soft coke formation occurs. When the temperature is too high the coke formed generally is very hard and difficult to remove from the coke drum with hydraulic decoking equipment. The temperature is used to control the Volatile Combustible Matter (VCM) of coke. At higher temperature VCM is reduced.

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Effect Of Coke Drum Pressure

Coke yield decreases by reducing coke drum pressure. Every 0.5 kg/cm2 reduction in coke drum pressure increases liquid yield by 1.3% vol and reduces coke yield by 1 % wt of fresh resid feed. For producing premium grade coke, coke drum should operate at higher pressure. Raising the pressure suppresses vaporisation of gas oil in the coke drum. It extends the retention time of aromatic compounds which favours the formation of better quality coke. Higher pressure improves the coke quality w.r.t lowering of Coefficient of Thermal Expansion (CTE) and electrical resistivity.

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Effect Of Recycle Ratio (RR)
Increase in Recycle Ratio (RR) increases coke make and improves coke properties. Increase in Recycle Ratio lowers the combined feed resin asphaltene content and in turn also provides a higher concentration of aromatics in coke drums. High RR Results in more coke, more gas & gasoline, less distillate, less deposition of coke in heater tubes. Low RR Results in less coke, less gas & gasoline, more distillate, more deposition of coke in heater tubes. HCGO quality deteriorates at lower RR w.r.t its density, CCR, metal content, end point etc. Modern Cokers operate at 10% or less RR to increase unit throughput.

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PRESENTATION ON DELAYED COKER

Effect Of BFW Injection in Heater Coils

Used as a turbulising water in heater coils. Reduces partial pressure of hydrocarbon in the coke drum. Leads to formation of loose coke. Normally turbulising water is kept @ 1% of pass flow. However, it depends on heater design.

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PRESENTATION ON DELAYED COKER Summary of Impact of Operating Parameters

Increasing Pressure Recycle Rate Coil Temperature Velocity Medium Gas Yield C5 + Liquid Yield Coke Yield HCGO Quality Improves Improves Deteriorates Deteriorates

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PRESENTATION ON DELAYED COKER Process Licensors of Delayed Coker

Some of the well known process licensors of Delayed Coker Unit are as under Foster Wheeler Lummus Technology Conono Philips Exxon Mobil etc.

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PRESENTATION ON DELAYED COKER

Safety Hazards & Mitigation

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PRESENTATION ON DELAYED COKER Delayed Cokers Safety Hazards :

Coke drum switching Severe accidents reported due to faulty valve operation during coke drum switching operation. Coke drum head removal Hot eruptions due to inadequate coke bed cooling. Incomplete draining before bottom head removal. Avalanche of shot coke during bottom head removal. Coke cutting operations Cutting tool raised out of coke drum without isolation. Bursting of water hose. Failure of wire rope supporting the drill stem. Others Dust irritation, toxic exposure, coke handling by o/h cranes, conveyors, crushers pay loaders etc.
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PRESENTATION ON DELAYED COKER Delayed Cokers Mitigation of Safety Hazards :

Coke drum switching Remote operated system for removing faulty operation. Colour coding of valves to avoid faulty operation. Employees working in pair buddy system Coke drum head removal Remote opening/ closing of coke drum head. Restricted movement of people on coke drum top and bottom platforms. Coke cutting operations Interlocks to prevent drill stem to come out of the coke drum w/o isolation. Remote switch off for jet pump.

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PRESENTATION ON DELAYED COKER

Modern Delayed Cokers Design Features

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PRESENTATION ON DELAYED COKER Modern Trend in Delayed Coker Technology

Maximize the production of liquid distillate. Minimize the production of coke. Produce heavy gas oil suitable for downstream catalytic processing. Optimize number and size of coke drums. Optimize energy recovery. Optimize feed pre-heat system and heater duty. Maximize air cooling and minimize water cooling. Low pressure operation i.e 1.05 kg/cm2-g drum pressure. Reduction in Recycle Ratio (10% or lower) for maximizing distillate yield. High CCR feed processing.
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PRESENTATION ON DELAYED COKER Modern Trend in Delayed Coker Technology

Shorter coke drum cycle (18 hours or lower). No sloping from blowdown. Refinery slop (with reactor o/h quench) and sludge (during coke drum quench) processing. Increased heater run length ( 1 Yr +) and online spalling. No quench column/ RFO generation. Double fired heater with online spalling and decoking facility. Automatic heading and deheading system. Hydrocyclone for recovery of coke cutting water.

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PRESENTATION ON DELAYED COKER In NUTSHELL

Delayed Coking is an attractive option for upgradation of residual fractions. Coking is a severe thermal cracking process aimed at distillate and lighter production during which coke is also formed. Modern trend is to go for low recycle, low pressure Delayed Cokers for maximizing liquid yield.

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PRESENTATION ON DELAYED COKER

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