Hyt 4 2017

Cracking
Dissociation of high molecular weight hydrocarbons into

smaller fragments.
Cracking
Residence time, s: <0.6, 1 to 6, 10-20

Recycle Ratio or per pass conversion
Coke formation: Very high, Catalyst reg. 2 to 6 s, 1 yr
Nature of reaction: Endo, Endo, Exo
THERMAL CRACKING
Factors affecting Thermal Cracking
Very high due to low conversion & optimized

residence time
Challenges in Thermal Cracking
- Over cracking
- Uncontrolled reactions
- Significant coke formation
- Low residence time has to be maintained
- Coke deposition leads decrease in conversion/through
put/poor product distribution
- MoC of pipe reactors
- High recycle ratio to optimize residence time vs over all
conversion
- Poor selectivity
CATALYTIC CRACKING
Widely used process in refinery
 Fluidized bed catalytic cracking (FCC)
 Moving bed catalytic cracking (being replaced by FCC)
Purpose: Heavy oils into gasoline and light olefins
Feed: Atmospheric gas oil (AGO), vaccum gas oil (VGO), coker gas oil,
vaccum residue (20%)
Catalysts:
 Zeolites (highly acidic) X&Y type
 ZSM-5 (Zeolite Socony Mobil–5)
 Pt/zeolites (Pt for CO-CO2 in regeneration)
3. Fluid Catalytic Cracking (FCC), Most preferred process
Reactor: Cracking Reactions
Regenerator: Coke (C) to CO2 & CO to make catalyst carbon free

Thermofor
moving bed
catalytic cracker
Catalyst particle size ≈ 1 cm
Co-current vs Counter current flows

Houdri moving
bed catalytic
cracker
Advantages:
• Low maintenance cost
• High cost activity
• Flexibility in charged
stocks and conversions
Fluidized bed (fluid)
catalytic cracking (FCC)
or FCC Riser-Reactor or
Flexi FCC
Steam
Vapour & Solid
(50 μm liquid droplets)

Heavy HC (Liquid)
Typical capacity:
H.P. Refinery, Bombay: 7500 B/day.
Cat. Circulation : 8 T/hr.
Cat. Hold up : 15 T cracker
19 T Catalyst in Regenerator
Catalyst Particle size : 40-80 m
S.A. = 500 m2/g of fresh & 200 m2/g of spent catalyst
R.T. = 465-5100 C
P = 1.5 atm
Sinopac Corporation, China
II Catalytic Cracking Catalysts

1Catalytic Cracking Desulphurization Additive
MS011
2Catalytic Cracking Propylene-Increasing Additive
(1) MP051 for Catalytic cracking propylene-increasing
additive II
(2) MP031
(3) CHPA
3Catalytic Cracking Gas-Increasing Additive
CAseries
Propylene yield up to 20%

Lewis Site
Bronsted Site
• Bronsted acid sites are responsible for the cracking

• During reaction B-sites are converted into L-sites
• Using steam in Regenerator L-sites are converted back to
B-sites
Reactor variables for FCC:
Temperature: RT : 450- 520 0C

Regenerator temp: up to 7000C
‘No Net Heat Addition’
Regenerator
C + O2 → CO2 + CO, ΔH = negative
Heated catalyst Particles from regenerator are used to exchange
heat with preheated feed to achieve reactor temperature and
heat of cracking reactions.
H.T. → olefins (C3,C4)
M.T. → gasoline
L.T. → Improper cracking
Short contact time → high reactor temperature can be
maintained.
Pressure: 1.5 atm or so, As such no effects
L.P ↑ ‘C’ formation
H.P. ↓ light H.C.
Riser contact time: 2 to 6 sec
Short contact time and high temperature give High O.N.
compounds.
Catalyst to oil ratio: 2 to 7

Ratio has to be varied over the period of time due to ↓ in catalytic
activity with usage of it even if regenerating the catalysts. For fresh
catalysts keep the ratio 2 to 3.
As slip velocity ↑ contact between vapour and particles is poor

→ Improper cracking.
Heat balance:
Breakdown of FCC Heat Requirements
Heat consuming event % of Total
Heat up and vaporize fresh feed 40-50%
Heat for recycled oil 0-10%
Heat of reaction (ΔH= +ve) 15-30%
Heat: steam 2-8%
Heat : losses 2-5%
Heat: air to regeneration temp. 15-25%
Heat: Coke temp from Reactor temp to 1-2%
Regeneration temp
Hydrocracking
H2 + Catalyst + Heat → Hydrocracking
Hydrocracking is an Exothermic Reaction
Hydrocracking deals with cracking of heavy feed stock to get

the products like Diesel, Gasoline, Naphta, & Fuel oil. In
addition to it, Hydrocrakcing removes S,N,O,M-impurities
hence eliminate Hyrdotreater.
Purpose: Heavy H.C. to lighter H.C.
Feed: VGO, AGO, HGO, LGO, visbreaker gas oil, FCC residue.
Products: Naphtha (gasoline), Diesel, Kerosene, Jetfuel, Olefins.
Licensors: Axens, Exxon Mobil
Shell global solution, UOP

Catalysts: Ni-Mo or Ni-W on Zeolite
Ni-Mo or Ni-W on amorphous silica alumina
Pd on Zeolite
Catalyst life: 1-2 yrs, Very low Coke deposition compared to FCC
Catalytic Reaction Conditions:
Reactor temp.: 315-4250C, Pressure: 50-80 atm.
Conversion: 60-80%
Typical Reactions:
[Cracking reactions like FCC ]
Hydrocracking of parrafins R-R’ + H2 → RH + R’H
Aromatic saturation
Isomerization n-R.H → i-R-H
Dealkylation of Aromatic Rings
Additional reactions: HDS, HDN, HDO, HDM Impurity Removal.
Coke formation:
Due to H2 presence, coke formation is slow or very less. The
high pressure of system also help in reducing coke formation.
Without regeneration catalyst can be used for 1 yr.
Reactors:
Trickle Bed Reactor:
Trickle Bed Reactor: {H.C.(liq.) + H2 (gas)} reactants are pass-down
over a fixed bed of catalysts.
Ebullated Bed Reactor:

Bubbling or Ebullating Fluidization
Once -Through Trickle Bed Hydrocracker
 Hot water is injected to remove NH3 & H2S

 Series of fractionators are used to separate L.N, H.N, middle
distillates & unconverted oil.
 Feed B.P. range: 340-5500C , API: 22, Sp.g.r. : 0.922, S=2.5%,
N:950 ppm.
 Product quality: Research O.N. 79-80 (Heavy Naphtha)
Jet fuel: Flash point: 380C , Smoke point: 34mm, Aromatics: 7%.
Diesel: Cetane No: 55, flash point: 520C.

Ebullating Bed
Hydrocracker
Ebullated bed can treat Residual oils (ADU, VDU etc)
Ebullated bed provides turbulent mixing of all three

phases→ better H.T., Uniform temperature
Conversion up to 90%
Better quality of products
on
, Moving Bed
Moving Bed
Continuous-Regenerative Catalytic Reforming (CCR)

Alkylation
Objective
Alkylation processes combine light olefins (primarily
propylene and butylene) with isobutane in the
presence of a highly acidic liquid catalyst.
The product (alkylate) contains a mixture of high-

octane, branched-chain paraffinic hydrocarbons.
Hydrofluoric Acid (HF) Alkylation
Coking
Delayed coking, Semi-batch Process
Fluid-bed coking, Continuous Process
Delayed Coking:
In a delayed coker, vacuum residue feed is heated to
about 487 to 520°C and sent to a large coke drum.
Cracking begins immediately, generating coke and
cracked, vaporized products. Coke stays behind in the
drum while the vapors rise to the top and flow to the
product fractionator.
Liquid products include coker naphtha, light coker
gas oil (LCGO), and heavy coker gas oil (HCGO).
Hot residue keeps flowing into the drum until it is
filled with solid coke
Typically, coke drums operate on 18- to 24-hour
cycles, which include preheating the drum, filling it
with hot oil, allowing coke and liquid products to
form, cooling the drum, and decoking.
Coke can account for up to 30 wt% of the product.
Electrodes made from Petcoke of Indian Crude is best

seller across the World
Use of Patcoke alternative to NG and Liquid HC Fuel

Fluid Coking
Alternative Fuels
5% Ethanol
Blended gasoline
in India
Can Japan burn flammable ice for energy?
CNN, November 2, 2017
Worldwide there are up to 2,800 trillion cubic meters

of Ice Gas trapped in methane-bearing gas hydrates (a
frozen mixture of water and natural methane)
according to the United States Energy Information
Administration.
Vast reservoirs of this resource are found where high

pressures and low temperatures combine -- i.e. under
deep ocean floors.
Scientist holds marine natural gas hydrate trapped in icelike crystals,
extracted from the seabed of the Shenhu Area of the northern South China
Sea. Similar marine natural gas hydrates have been extracted from Japan.
These ice crystals hold a remarkable quantity of natural methane gas. It is

estimated that one cubic meter of frozen gas hydrate contains 164 cubic
meters of methane.

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Cracking

Dissociation of high molecular weight hydrocarbons into

Residence time, s: <0.6, 1 to 6, 10-20

Very high due to low conversion & optimized

Reactor: Cracking Reactions

Regenerator: Coke (C) to CO2 & CO to make catalyst carbon free

Catalyst particle size ≈ 1 cm

Co-current vs Counter current flows

(50 μm liquid droplets)

II Catalytic Cracking Catalysts

Propylene yield up to 20%

• Bronsted acid sites are responsible for the cracking

Temperature: RT : 450- 520 0C

Catalyst to oil ratio: 2 to 7

As slip velocity ↑ contact between vapour and particles is poor

H2 + Catalyst + Heat → Hydrocracking

Hydrocracking is an Exothermic Reaction

Hydrocracking deals with cracking of heavy feed stock to get

Products: Naphtha (gasoline), Diesel, Kerosene, Jetfuel, Olefins.

Licensors: Axens, Exxon Mobil

Shell global solution, UOP

Ni-Mo or Ni-W on amorphous silica alumina

Catalytic Reaction Conditions:

Reactor temp.: 315-4250C, Pressure: 50-80 atm.

Ebullated Bed Reactor:

 Hot water is injected to remove NH3 & H2S

Diesel: Cetane No: 55, flash point: 520C.

Ebullated bed provides turbulent mixing of all three

Continuous-Regenerative Catalytic Reforming (CCR)

The product (alkylate) contains a mixture of high-

Coke can account for up to 30 wt% of the product.

Electrodes made from Petcoke of Indian Crude is best

Use of Patcoke alternative to NG and Liquid HC Fuel

Worldwide there are up to 2,800 trillion cubic meters

Vast reservoirs of this resource are found where high

These ice crystals hold a remarkable quantity of natural methane gas. It is

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