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Pre 4 2025 SSP

The document discusses various cracking processes in petroleum refining, including thermal cracking, catalytic cracking, and hydrocracking, highlighting their mechanisms, challenges, and advantages. It details the types of catalysts used, operational conditions, and the products generated from these processes. Additionally, it covers the importance of controlling coke formation and optimizing residence time for efficient conversion of heavy hydrocarbons into lighter products.

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Preet Tapiawala
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10 views53 pages

Pre 4 2025 SSP

The document discusses various cracking processes in petroleum refining, including thermal cracking, catalytic cracking, and hydrocracking, highlighting their mechanisms, challenges, and advantages. It details the types of catalysts used, operational conditions, and the products generated from these processes. Additionally, it covers the importance of controlling coke formation and optimizing residence time for efficient conversion of heavy hydrocarbons into lighter products.

Uploaded by

Preet Tapiawala
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Cracking

Dissociation of high molecular weight hydrocarbons into


smaller fragments.
Cracking
THERMAL CRACKING
& Dealkylation
+ CH3.
Challenges:
• Uncontrolled Cracking
• Coke Removal
Factors affecting Thermal Cracking

Around 1 s
Very high due to low conversion & optimized
residence time

Per pass conversion around 30%


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 (almost 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)
Length Scales in Heterogeneous Catalysis

Mass transport/diffusion Chemical


adsorption and
reaction
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

Air
Air

Co-current vs Counter current flows


Houdri moving
bed catalytic
cracker

Advantages:
• Low maintenance cost
• High cost activity
• Flexibility in charged
stocks and conversions
Fluidization
Fluidized bed (fluid) (Products)
catalytic cracking (FCC)
or FCC Riser-Reactor or
Flexi FCC

700 oC
500 oC
Steam
Vapour & Solid

Heavy HC (Liquid)
(50 μm liquid droplets)
Typical capacity:
H.P. Refinery, Bombay: 7500 B/day (830 L/min) + Recycle.
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

VGO: IBP 300 oC, FBP: 550 oC


(Recycle)

(Recycle)
Catalyst: Zeolite is crystalline Alumino-silicate material
• Al and Si atoms form tetrahedral, which are linked by shared
oxidation atoms
• More than 1000 zeolites are available : Natural and Synthetic
• As Alumina increases, Acidity increases
• Zeolites have high adsorption capacity as well
• High S.A. 300 to 500 m2/g
• High acidity
• Favourable for catalytic cracking
• Pore size: 60-80A0. Too low pore size causes the problem in ‘C’
removal, where as large pore size decreases cracking
X & Y Zeolites are used for FCC

NaP AlpSi102.pO384.gH2O
p = 96 to 74 for X zeolite
74 to 48 for y zeolite
g = 250 to 270 as Al ↓
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
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%


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 Good 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 (IFP) Exxon Mobil
Shell global solution UOP
Catalysts: Ni-Mo and/or Ni-W on Zeolite
Ni-Mo and/or Ni-W on amorphous silica alumina
Pd on Zeolite
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
Ebullated Bed Reactor
Trickle Bed Reactor: {H.C.(liq.) + H2 (gas)} reactants are pass-down
over a fixed bed of catalysts.
Once -Through Trickle Bed Hydrocracker
• Hot water 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: 34 mm, 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
Cracking

Residence time, s: <0.6, 2-6, 10-20


Recycle Ratio, 2-4 1.5-2 -
per pass conversion, 30% 70% 90%
Coke formation, Very high Catalyst reg. 2 to 6 s, Very low, 1 yr
Nature of reaction, Endo Endo Exo
Phases, Gas Gas-Solid Gas-Liquid-Solid
Reactions: (Mostly Endothermic)

Isomerization:
Semi-regenerative Catalytic Reforming (SRR)

Catalyst is regenerated in situ during routine catalyst regeneration shutdowns which occur
approximately once each 6 to 24 months. Such a unit is referred to as a semi-regenerative
catalytic reformer (SRR). Mo and Co based catalysts are used in SSR.
Continuous Catalytic Reforming (CCR)

Pt based Catalysts require continuous regeneration therefore instead of waiting for periodic
shut down, catalysts are continuously regenerated.
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.
✓ Products include gases, 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 h cycles,
which include preheating 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
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.
HF BP 19.5 oC

Hydrofluoric Acid (HF) Alkylation

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