Cracking and Coking operations

MODULE – 3
PART 1
 THERMAL CONVERSION PROCESS
• Process in which hydrocarbons are
decomposed at elevated temp to form
material of lower molecular weight are called
thermal conversion process.
• 1.Visbreaking (425 – 460C)
• 2.Thermal cracking (460 – 500 C)
• 3.Coking (520 -600 C)
• Reaction-
• 1.Cracking
• 2.Dehydrogenation
• 3.Hydrogenation
• 4.Saturates to unsaturates
• 5.Ring opening (extreme condition)
• Reaction mechanism-
• Free radical mechanism- reaction proceeds via free radical
mechanism. Free radicals are atom or group of atom with
bare unpaired electron. Unpaired electron are very active
and try to form stable compound by acquiring unpaired
electron from sources available.
• Initiation
• Propagation
• Termination
• Stability of radical decrease with increasing size
of molecule.
• Factors affecting reaction-
• 1. Temperature
• 2. Pressure
• 3.Residence time
• 4. Feed stock characteristics.
 Visbreaking
• The VR obtained from vacuum distillation is
viscous, there fore it must be blended with
sufficient quantity of diluents or cutter
stock(light gas oil) for reducing its viscosity.
Visbreaking process has been found to be a
good process to reduce the consumption of
diluents, and we get LPG and naphtha.
• 1. conventional visbreaking(coil)
• 2. Soaker visbreaking
• The gas oil fraction produced by visbreaking is
also used to increase catalyst cracker feedstocks
and increase gasoline yeild.
• To reduce the viscosity and pour point of VR to
meet fuel oil specification.
• Long paraffinic side chain attached to aromatic
rings are the primary cause of high pour point
and viscosities for paraffinic base residue.
• Visbreaking is carried out at to breaking of these
long side chain and their subsequent cracking.
• The objective is to reduce the viscosity as
much as possible without significantly
affecting the fuel stability.
• The degree of viscosity and pour point
reduction is a function of composition of
feedstocks. Waxy feed stocks achieve pour
point reduction from 8 to 20C and final
viscosity from 25 to 75% of the feed.
• The principal reactions are
• 1. cracking of side chain attached to
cycloparaffin and aromatic rings.
• 2. Cracking of resins to light hydrocarbons
primarily olefins.
• 3. At temp above 480C some cracking of
naphthene rings.
• Viscosity breaking, is a mild liquid phase
thermal conversion process to reduce viscosity
of atm and vacuum residue to produce
specification of Fuel oil.
• Small quantity of L.P.G and fair amount of
Naphtha are also produced.
• Temp (425 – 460 C)
• Pressure (4 – 20 atm)
 Process variables
• Furnace outlet temp- cracking increases with
increase in furnace outlet temp, coke laydown in
furnace tube is also increased.
• Furnace outlet pre- high pre supppresses
vaporization and tends to produce a liquid phase.
• Feed rate – severity of visbreaking operation
decreases with increase in feed rate for the same
furnace outlet temp.
• Feed stock characterestics-
• Compounds in visbreaker feed may be considered
as
• 1. colloidal asphaltene particle, it is non volatile
and difficult to crack.
• 2. volatile heavy hydrocarbon- hold the
asphaltene in colloidal suspension.
• NC5 insoluble content- normal pentane to extract
the hydrocarbon oil and leaving the insoluble
asphaltene. Increase of NC5 insoluble content in
the feed, viscosity of feed and yeild of visbroken
residue increase.
 Typical operating condition
• Furnace inlet temp – 340C
• Furnace outlet temp- 470 to 490C
• Furnace inlet pre – 22 Kg/cm2
• Furnace outlet pressure- 15 kg/cm2
• Residence time – 600s
• Quench temp – 260C
 Comparison of Coil visbreaking and
Soaker Visbreaking
• Coil Visbreaking-
• Higher furnace outlet temp and reaction time
from 1 to 3 min.
• Shorter run time between start up and decoking
of furnace (3 to 6 months).
• Soaker Visbreaking-
• Lower furnace outlet temp and longer reaction
times.
• Lower energy consumption.
• Longer run times (6 to 18 months).
 Advantages of Soaker visbreaking
• Lower capital expenditure
• Smaller furnace
• Less waste heat recovery equipments
• Lower pressure drop through the furnace
• Lower fuel consumption
• Better or more selective yeild.
 Decoking of furnace tube
• During cracking operation some of the olefinic
compounds polymerize to form coke which is
deposit inside the tube wall. The coke lay down
increase the tube skin temp and pressure drop.
• Decoking with steam and air is called spalling
and burning.
• During spalling, steam is admitted into furnace
tube while they are being fired. 80 to 90% coke is
removed.
• Burning period injecting both steam and air, the
air ignite and consume coke.
 THERMAL CRACKING
• Earliest method used by refiners to get greater
yield of light distillates from a given crude oil.
• The products of thermal cracking have poor
stability and require further treatment
• This process produce gas, naphtha, middle
distillates. Gas produced from thermal
cracking contain propylene and butylenes.
• Temp (520C)
• Pressure (25 – 35 atm)
Thermal cracking
 Process description
• The feed is heated in the furnace to the cracking temp
of 450 -500C and the cracked products containing gas
and distillates enter the fractionator after passing
through an intermediate separator vessel. In the
fractionator gas, naphtha and gas oils are separated.
The fractionator bottom and the separator vessel
bottom products form the residual fuel oil.
• In the two coil operation heavy distillates from the
fractionators is withdrawn and further cracked in a
separate furnace and cracked products are fed to the
bottom of the fractionators.
 Coking
• Coking units convert heavy feed stocks into solid
cocks and lower boiling hydrocarbon products,
which are suitable as feed stocks to other refinery
units for conversion into higher value
transportation fuel.
• The coke formed contain some volatile matter or
high boiling HC.
• To eliminate all volatile matter, it must be
calcined (1000C).
• Coking – to pretreat VR to prepare coker gas oil
streams suitable for feed to FCCU/HCU.
 Types of Coke
• All cokes produced from coker is called green
coke. (fuel grade coke) or sponge coke.
• Calcined coke – make anodes for Al or steel
production.
• Needle coke – microscopic elongated crystalline
structure. Produced from highly aromatic feed
stocks, operating at high pre and high recycle
ratio. Needle coke is preferred over sponge coke
for use in electrode manufacture.
• Shot coke- undesirable, during any process
upsets.
 Uses of Coke
• Fuel
• Manufacture of anodes
• Direct use as a chemical carbon source. Cac2
and SiC.
• Manufacture of electrodes for use in electric
furnace.
• Manufacture of graphite.
 COKING
• More severe form of thermal cracking. It is
less expensive way to get more light distillate.
Petroleum coke is a by product, for the
manufacture of electrodes and aerospace
components.
• 1. Delayed coking
• 2.Fluid coking
• 3. Flexi coking
 Delayed coking
• Increasing production of Diesel oils and to
produce low sulphur petroleum coke.
• Thermal cracking reaction extended to a
period of 24 hrs in a coke drum.
• Temp (550 C)
• Pressure (1- 7 atm )
DELAYED COKING
• Hot fresh liquid feed is charged to the fractionator two
or four trays above the bottom vapour zone.
• Hot vapours from the coke drum is quenched by the
cooler feed, prevent the coke formation in the
fractionator and simultaneously condensing a portion
of the heavy ends.
• Any remaining material lighter than the desired coke
drum feed is stripped from the fresh liquid feed.
• The fresh feed is preheated and it is more energy
efficient.
 Process Description
• Fresh feed is charged through HE (coker
distillates) to the lower portion of the main
fractionator where it contacts the heated vapours
from the coke drum and light components are
flashed off from the feed. The heavy residue from
the bottom of the fractionator is passed through
a furnace where it is heated to a temp in the
range of 480 to 515C and charged to one of two
coke drums. One in operation for coke
accumulating and the other out of service for
hydraulic decoking.
• Coke drums typically range in dia from 4.5 to
8.5 m and in height from 25 to 35 m. The
material fed to the coke drum is thermally
decomposed. As the cracking reactions are
endothermic, the temp in the coke drum is
lower than at the furnace outlet and usually is
in the range of 415 to 460C. Pressure in the
coke drum varies from 1 bar to 7 bar.
• In the coke drum sufficient time is allowed so
that the reaction proceeds to form coke which
is settled in the coke drum.
• Lighter cracked products from the coke drum
are returned to the fractionator. In the
fractionator , gas, naphtha, kerosine and gas
oil are separated from heavier materials which
is recycled with fresh feed.
• When the coke build up to predetermined level,
the flow is diverted to another coke drum.
• At the end of each cycle the coke drum is
depressurized and steamed out to strip
uncondensed vapours. The coke drum is finally
cooled with water and the top and bottom heads
are opened up for cutting the coke. Coke cutting
is done by high pressure water jet (135 to 275
kg/cm2).
 Mechanism of coking
• 1. very high molecular weight compounds, such
as asphaltenes and resins tends to dealkylates to
straight chain compounds and methylene groups
when subjected to high temp. This leads to a
residue of carbon with highly disordered, cross
linked structure or with many graphite crystals.
• 2. depends upon the dehydrogenation of heavy
oils. The subsequent polymerization of free
radicals forms high molecular weight compounds
with high carbon to hydrogen ratios which
proceed eventually to coke.
 Process variables
• Temp- coke drum temp is used to control the
VCM (volatile combustable material) content
of delayed coke.(6 to 8%).
• Pressure – low pressure is favoured.
• Recycle ratio = recycle feed+ fresh feed/fresh
feed.(1.1 to 2)
• Feed stock characterestics-
ccr,API,asphaltenes, resins,
• Coke yeild = 2+1.66*CCR wt%
 Products of Coker
• Gas
• Light naphtha
• Heavy naphtha
• LCGO
• HCGO
• Coke
Flexi Coking
 Flexicoker
• The feed is preheated to 315 to 370C and sprayed
into the reactor, where it contact a hot fluidized
bed of coke. This hot coke is recycled to the
reactor from the coke heater to maintain the
reactor bed temp between 510 to 540C and
provide the heat for cracking reaction.
• The cracked vapour products passed through
cyclone separators and are then quenched in the
scrubber vessel located at the top of the reactor.
• Some of the high boiling cracked vapours are
condensed in the scrubber and recycled to the
reactor.
• The rest of the cracked vapours are flow to the
fractionator, where various cuts are separated.
Wash oil circulated over baffles in the scrubber
provides quench cooling.
• The coke produced by cracking is deposited as
thin film on the surface of existing coke particles
in the reactor fluidized bed.
• The coke is stripped with steam and flow to
the heater where it is reheated to about 593C.
The coke heater is also fluidized bed and its
primary function is to transfer heat from the
gasifier to the reactor.
• Coke flows from the coke heater to a third
fluidized bed in the gassifier, where it is
reacted with air and steam to produce fuel gas
consists of CO,H2 ,CO2 and N2.
• The gas flow from the top of the gasifier to the
bottom of the heater to fluidize the heater bed
and provide the heat needed to the reactor. The
reactor heat requirement is supplied by
recirculating hot coke from the gassifier to the
heater.
• The coke gas leaving the heater is cooled in a
WHB, passed through a external cyclone and a
venturi type wet scrubber. After removal of
entrained coke fines, the coke gas is treated for
removal of H2S and then used as refinery fuel.
 Fluid coking
• In fluid coking process, only enough of the
coke is burned to satisfy the heat
requirements of the reactor and the feed
preheat.
• Only two fluid beds are used in a fluid coker, a
reactor and a burner, which replaces the
heater.