An Introduction to Delayed Cokers

By A S Sahney PNM, IOCL-PR

Topics of Discussion

Thermal Cracking - overview Delayed Coker FIT in overall Refinery Feed stock Process Products Coke formation & types of Coke Coke Drum Cycle Operating Variables Safety Hazards Modern Delayed Coker design features

Delayed Cokers Thermal Cracking

Essential requirement for upgradation - Improve properties e.g. increasing H/C ratio Carbon rejection and hydrogen addition processes Catalytic and non Catalytic processes Hydrogen and Non-Hydrogen based processes Thermal (conversion) and solvent based (separation processes)

Routes for upgradation

Why Thermal Cracking ?

Residual fractions (Bottom of the barrel ) and heavy oils etc. are least valuable streams of a refinery Nearly 50% of the typical crude oils processed in INDIAN refineries contain 370 OC+ fraction Worldwide limited reserves of sweet CRUDES Disposal problems due to stringent environmental norms Decreasing demand of fuel oils Simultaneous increasing demand of middle distillates

THERMAL CRACKING

THERMAL CRACKING AND ITS ADVANTAGES

SIMPLE AND COST EFFECTIVE PROCESS

CATALYTIC CRACKING
PRESENCE OF HIGH MOLECULAR WEIGHT COMPOUNDS e.g. RESINS, ASPHALTENES AND METALS IN RESIDUAL FEEDSTOCKS MAKE IT UNSUITABLE FEED FOR CAT CRACKING METALS AND SULFUR COMPOUNDS ACT AS CATALYST POISONS

VARIOUS THERMAL CRACKING PROCESSES

VISBREAKING

DELAYED COKING FLUID COKING FLEXI COKING

Thermal Cracking Reactions

Thermal cracking reactions take place only as an effect of heat. During the cracking, large molecules decompose and form smaller (lighter) molecules Generally, two types of reactions take place Primary reactions, in which decomposition of large molecules to smaller molecules takes place. Secondary reactions by which active products from primary cracking reactions further crack or react to form other compounds, or polymerize to give heavy products

Delayed Cokers FIT in a refinery

Where does Delayed Coker fit in a refinery ?

Where does Delayed Coker fit in a refinery ?

Primarily processes VR from primary units Proven technology for converting heavier refinery streams into lighter products Extremely flexible in processing a vide variety of crude oil slates Increases distillate yield for the Refinery and minimizes or eliminates Heavy fuel oil production Simple and cost effective thermal cracking process as compared to other upgrading options

Delayed Cokers in INDIA

Operating Coke Drums Forthcoming Coke Drums
IOCL, G,M,P CPCL BORL Bhatinda RIL Essar MRPL HPCL/ BPCL Total (Approx)

Digboi Guwahati BRPL NRL Barauni Panipat RIL total

2 2 2 2 6 4 8 26

2,2,4 2 2 2 8 6 4 2 34

Delayed Cokers PROCESS

Delayed Cokers Feedstock

Delayed cokers can process a wide variety of feedstocks

Can have considerable metals (Ni and V), Sulfur, resins, and asphaltenes Most contaminants exit with coke

Typical feedstock VR, Refinery Slops, Sludge Atm. Residue occasionally used Typical Feed composition
6 % Sulfur 1,000 ppm (wt) metals CCR of 20 30 wt.%

Feed ultimately decides the type of Coke obtained from the process

Delayedprocess Cokers - Process Only batch-continuous

in a refinery Flow thru the furnace coils is continuous while the feed is switched between two coke drums On-line drum is getting filled with Coke while the off-line drum is going thru steam stripping, cooling, decoking, pressure testing, warm-up etc. Overhead vapors from the Coke drums flow to the fractionator Fresh feed combines with the condensed product vapors (recycle) in the fractionator bottom and forms furnace feed

DELAYED COKING

Delayed Coker - Products

GAS PRODUCTS
Fuel gas (H2, C1, C2) LPG (C3, C4)

LIQUID PRODUCTS
Naphtha - highly olefinic Light Gas Oil Diesel component (requires hydro-treating) Heavy Gas Oil Hydro-cracker feed

Petroleum Coke

Delayed Cokers COKE

Coke Formation

Delayed Cokers Chemistry of Coking

Carbon rejection Process

Coke has very little H2 shifts to the lighter streams Metals, Sulphur concentrate in coke

Cycle of cracking and combining

Side chains crack-off of Polynuclear aromatic (PNA) cores and generally end up in light streams PNAs combine (condense) to form coke. Metals and

hetroatoms in PNA core generally end up in coke

Conditions
High temperature and low pressure favor cracking High residence time favors the combining reactions

Delayed Cokers Chemistry of Coking

Cracking Reactions
Saturated paraffins crack to form lower MW olefins & paraffins Side chains cracked off small rings aromatics, cycloparaffins (naphthenes) & Polynuclear aromatics

Combining reactions
Low MW olefins form higher MW compounds small rings aromatics combine to form resins Resins after cracking off side chains combine their remaining Polynuclear aromatics to form asphaltenes Asphaltenes after cracking off side chains left with large PNAs

The large PNAs precipitate to form crystalline liquids and ultimately solidify to form coke embedded with Metals & Sulphur

Delayed Coker Types of Petroleum Coke

Sponge Coke
Porous, irregular

Needle Coke
Needle like

Shot Coke
Undesirable

shaped Feed moderate Asphaltene High S - fuel grade Low S Anode grade

structures Feed high Feed low S, very Asphaltene low Asphaltene Difficult & unsafe Premium grade to handle Coke Very low CTE

Delayed Cokers Typical Product Yields

Delayed Coker Product Yields

Coke and liquid yields from a typical Delayed Coker unit may be estimated by simple imperical equations as under
Coke Yield (wt %) = 1.6 x (wt % CCR) Gas (C4 - ) (wt %) = 7.8 + 0.144 x (wt % CCR) Gasoline ( wt % ) = 11.29 + 0.343 x (wt % CCR) Gas Oil (wt %) = 100 (wt % Coke) (wt % Gas) (wt % Gasoline)

Delayed Cokers Typical Product % Yields Yield % Case 1A Yield Case1B

Unit Feed Sweet Fuel Gas LPG Light Naphtha Heavy Naphtha LCGO HCGO CFO Coke H2S & Misc Arab Mix Crude ME Mix Crude No CFO No CFO kg/hr % m3/hr kg/hr % m3/hr 101 300000 100.00 322.83 300000 334.06 149 144 155 156 117 124 185 10715 9555 20865 4761 99272 61890 88980 3962 3.57 3.19 6.96 1.59 33.09 20.63 29.66 1.32 100.00 2916.6 9411 18.65 10595 30.44 22479 6.41 5615 118.73 115390 68.66 67563 66330 2617 3.14 2645.05 3.53 20.68 7.49 32.81 1.87 7.56 38.46 138.01 22.52 74.95 22.11 0.87 100.00

Delayed Cokers Coke Drum Cycle

Delayed Cokers: Typical Drum Cycle

Drum Cycle - Activities
Time (Hours)

Steam to Fractionator Steam to Blow down Low-range cooling & Water quench Depressurization & Drain Un-head Top and Bottom Drilling/ Cutting Re-head / Steam Purge/ Pressure Test Drum Warm-up (Vapor Heating) Change-over (Drum switch)

0.5 1.5 4.5 2.0 0.5 3.5 1.0 4.0 0.5

Delayed Cokers Drum Cycle

Steam Stripping

A critical activity before, during and after Coke Drum switch If Steam is not flowing in the Coke Drum feed line after the switch;
The un-solidified material (pitch) from bottom of Coke Drum will flow back in the feed line and restrict the flow of cooling water The unconverted feedstock on the top of coke bed will run down the channels in the coke bed and plug them. This results in isolation of the plugged sections of Coke bed from steam and cooling water. The hot-spots thus formed may result in potentially dangerous steam eruption during drilling/ cutting operation

Adequate Steam stripping helps to

Prepares the Coke bed for water cooling by bringing down Bed temperature to moderate level and by keeping the channels live Eliminates the pitch left in the bottom section of the coke drum Increases the amount of gas oil yield (middle distillates) Reduce the amount of volatile matter in coke (quality + loss)

Delayed Cokers Drum Cycle

Low range cooling & Water quench
Low range cooling follows the steam stripping. Small water is injected in to the Coke Drum without fully cutting-off the steam

Intermediate step approx. 1 hr Precaution avoid excessive hammering

Water quench is Big water cooling wherein water is filled in the Coke drum for complete Bed cooling

Duration 3-4 hrs Drum skin temperature are watched for confirmation

Depressurizing & drain

After adequate cooling, the Coke drum is depressurized and residual water is drained-out

Delayed Cokers Drum Cycle

Un-head Top & Bottom Covers

Drilling/ Cutting

Rehead/ Steam Purge/ Pressure Test

Delayed Cokers Drum Cycle

Drum Warm-up/ Vapor Heating

To prepare the cold empty coke drum for receiving fresh feedstock, hot vapors from online drum are routed into the empty drum The hot vapors at approx. 425 oC condense in the cold drum, heating the drum to a target temperature of around 340 oC Condensed vapors are continuously drained out of the drum After approx. 4-5 hrs of vapor heating, drum is ready to receive feed

Delayed Cokers Drum Cycle

On-Line Filling
After vapor heating the drum, hot oil from furnace at approx. 485oC is switched into the drum gradually in steps Most of the initial hot vapors condense on the colder wall of the drum, thereby heating the coke drum walls Once the coke drum is heated up properly, the drum top temperature starts increasing to achieve normal temperature of approx. 445- 450oC. Until the drum top temperature reaches normal value, the vapor load on the fractionator is also less than normal

Delayed Cokers Effect of Operating Variables

Transfer / coke drum temperature Pressure in coke drum Recycle ratio BFW Injection

Delayed Coker Operating Variables

Delayed Coker Temperature

Higher the Coke Drum inlet temperature, higher is the coke yield at constant pressure and recycle ratio 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 Higher Temperature reduces the volatile combustible (VCM) content of the coke

Delayed Coker Pressure

Coke yield decreases by reducing coke drum pressure. Each 0.5 kg/cm2 reduction in drum pressure increases liquid yield by 1.3% vol and cut in coke yield by 1.0% wt. of fresh RESID feed Higher the operating pressure, higher the coke make Higher pressure improves the coke quality primarily by lowering CTE and electrical RESISTIVITY but at the expense of liquid products

Delayed Coker Recycle Ratio

Higher the recycle ratio, higher the coke make Increasing the recycle rate lowers the combined feed resin ASPHALTENE content and in turn also provides a higher concentration of aromatics in coke drum Trend is to go for lower recycle ratio so as to increase throughput Low recycle ratio HCGO quality and more coke deposition in coils is a concern

Delayed Coker BFW Injection

Used as a turbulising water in Heater Coils Reduces partial pressure of hydrocarbon in the coke drum Leads to formation of loose coke

Delayed Coker Variables

Delayed Cokers Safety Hazards & Their Mitigation

Delayed Cokers Safety Hazards

Coke Drum Switching

Severe accidents have been experienced due to faulty valve operation during Coke drum switching operation

Coke Drum Head removal

Eruptions due to inadequate coke bed cooling Incomplete draining Avalanche of shot coke

Coke cutting operation

Cutting tool raised out of coke drum w/o isolation Water hoze bursting Failure of the wire rope supporting the drill stem

Others
Dust irritants, Toxic exposure, Coke handling by O/H cranes, conveyors, crushers, pay-loaders etc

Delayed Cokers Mitigation of Safety Hazards

Coke Drum Switching

Comprehensive remote operated system combining Interlocks & permissive for reducing faulty operation Colour coding of valve appropriately Employees working in pairs buddy system

Coke Drum Head removal

Remote opening/ closing of Coke drum head Restrict movement of ppl on coke drum top & bottom platforms

Coke cutting
Interlocks to prevent drill stem to come out of the Coke drum w/o isolation Interlocks for slack cable always ON Remote switch off for Jet pump

Modern Delayed Cokers Design Features

Modern Delayed Cokers Process Design Objectives

Maximize The Production Of Liquid Products Minimize The Production Of Coke Produce Heavy Gas Oil suitable for downstream Cat Processing Optimize Number And Size Of Coke Drums Optimize Energy Recovery Optimize Feed Preheat System And Heater Duty Maximize Air Cooling And Minimize Water Cooling

Modern Delayed Cokers Typical Process Features

Low Pressure Operation: 1.05 kg/cm2 Operating Conditions & Recycle Ratio Optimized to needs while maximizing Distillate Yield Low Recycle Operation: ~10% High CCR Feed Processing

Shorter Coke Drum Cycle ~18hrs No sloping from blowdown Total Water Reuse System Refinery Slop Processing Refinery Sludge Processing No Quench Column/RFO Generation No CFO Generation

Modern Delayed Cokers Typical Process Features

Modern Delayed Cokers Typical Process Features

Double Fired Heaters with Online Spalling & Decoking Facility Provision for Shot Coke Control & Handling Automatic Heading and Deheading System Efficient & Cost Effective Coke Handling Hydrocyclones for Recovery of water

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, in which coke is also formed. Trend is to go for low recycle, low pressure cokers so as to maximize liquid yield

SHOT COKE

SPONGE COKE

NEEDLE COKE