BITS Pilani

K K Birla Goa Campus

Alkylation, Isomerization and

Polymerization
 Alkylation - Introduction

04/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Alkylation - Introduction

04/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Alkylation - Introduction
• Developed in 1930 – 1940s to produce high octane aviation
gasoline but later used to produce gasoline

• Transfer of an alkyl groups from one compound (or molecule) to

other

• Important process as high quality (octane number) blending

component of motor fuels (gasoline) is produced

• Gaining importance over catalytic reformer (due to restrictions on

benzene and aromatic content in gasoline)

• Reverse of cracking
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04/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Feedstock and catalyst

• Feedstock
• Iso-butane and C3-C4 olefins produced as byproducts from FCC,
Hydrocracker and other catalytic and thermal conversion units
• Components (HCs) higher than butane are not desirable (due to
the resultant increase in boiling point)
• i-paraffin to olefin ratio – should be maintained at a higher values
(generally not less than 5)

• Catalyst
• Sulfuric acid (H2SO4)
• Hydrofluoric acid (HF)
• Aluminium chloride (Not commonly used) 5

04/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Reactions

• Carbonium ion mechanism

• Contact time: 30 – 60 mins
• Side reaction (Formation of complex
mixture of paraffins (heavies,
coke, etc.) Source: Pen State University (e-education site);
• Causes increased iso-butane consumption, Original source: Dr. Semih Eser

increased acid consumption, increased acid soluble red oil

formation,
• Can be controlled
• Maintaining proper composition of reaction mixture
• Maintaining adequate contact time and controlled temperature
• Having proper separation of reactor effluent
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04/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Important reaction conditions

• Reaction temperature
• H2SO4 alkylation: Requires low temperature (15 – 20 C) : to
prevent oxidation of the products
• HF alkylation: Operate upto temperatures of 35 C

• Other common operating conditions

• Volume ratio of catalyst to feed (should be 1)
• Strength of acids used
• i-butane to olefin ratio
• Olefin space velocity
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04/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Sulfuric acid alkylation processes

04/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Sulfuric acid alkylation processes

• Cascade H2SO4 alkylation process

• Reactor
• Cascade reactor with mixer (agitator) in each stage
• Isobutane and concentrated H2SO4 acid (85 – 95 %) are fed at the first stage
• Olefin is split and introduced in each stage separately
• Heat exchanger
• Caustic wash section
• Fractionator

04/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 HF Alkylation Process

• Reactor
• Feed: Olefin and isobutane (1: 5), HF acid
• Acts as a settler also
• Bottom: Acid (part of which is cooled and recycled back with fresh acid)
• Top: Alkylate and unreacted components (with some acid) sent to
fractionator
• Fractionator and stabilizer
• Alkylates, i-butane and acid are separated (as HF is slightly soluble in
hydrocarbon). Alkylate sent to stabilizer; i-butane recycled back.
• Stabilizer: alkylate and i-butane are separated and i-butane is recycled
back to the reactor
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06/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 HF Alkylation Process

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06/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Difference in H2SO4 and HF

• Properties
• Boiling point
• Freezing point
• Sp gravity
• Viscosity
• Solubility of i-butane in 100% acid
• Solubility of i-butane in 99.5% acid
• Solubility of acid in hydrocarbon layer
• Alkylate from HF process has higher octane number than
H2SO4 based process
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06/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Commercial alkylation technologies

• Exxon alkylation (H2SO4 based process)

• Stratco process (H2SO4 based process)
• ConocoPhillips ReVAP process (HF process)
• UOP HF alkylation (HF process)
• Lummus Alkyclean (Solid catalyst based process)

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06/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Challenges

• Corrosiveness of acids (liquid catalysts)

• Requires special materials of construction for the equipments
• Can lead to corrosion induced accidents and to various health
hazards
• Generation of waste water while recovering acids
• Replacing liquid catalyst with solid catalyst (but solid
catalyst has its own problems of deactivation, etc.)

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06/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Isomerization - Introduction

• Conversion of n-paraffins to isoparaffins

• Strategic gasoline process to maintain gasoline pool
octane and meet stringent gasoline quality requirement
• Demand for high performance naphtha isomerization has
increased because of its ability to reduce benzene conc.
• Last 20-25 years the isomerization capacity has increased
2-3 times (especially in Europe where it is almost
fourfold)
• It may take place in vapor phase or in liquid phase with
dissolved catalyst
• Improvement in octane no is of 8 units or more 15

06/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Feedstock

• Mainly C4, C5 and C6 fractions

• Higher carbon paraffins (n-heptane onwards)  tends to
crack

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06/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Catalyst
• Zeolite and chlorinated alumina
• Zeolite
• Requires high temperature and provides lower octane boost
• Generally platinum carried zeolite
• Regenerable
• Relatively contaminant tolerant but have lower activity
• Chlorinated alumina
• Results in higher octane
• Has sensitivity to feedstock impurities (water, S, N, O) and hence feed
need to be pretreated and also to be dried (need expensive driers)
• Highest activity and yield
• Need organic chloride feed
• Not regnerable
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06/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Process – Chlorinated catalyst -
fixed bed
• One reactor
• Catalyst promoter like hydrogen chloride continuously
added
• H2 atmosphere in reactor is essential to minimize coke
formation (Recycling of H2 as consumption is almost zero)
• Operating conditions (Reactor)
• Temperature : 150 – 190 C
• Pressure: 20 – 30 atm
• H2/HC ratio : 1.8 – 2.1
• SV: 2 – 3
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06/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Process – Chlorinated catalyst -
fixed bed

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06/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Process flow – fixed bed

• Desulfurized and moisture free feedstock with recycle n-

paraffins as feedstock, mixed with H2 and heated
• The HC-H2 mixture with recycled HCl gas fed to the
reactor containing alumina or bauxite
• Catalyst recovery system
• Pressure releaser – where H2 separates out
• Stripper – to recover HCl gas
• Caustic wash
• Fractionation – to separate i-paraffins from n-paraffins
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06/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Process flow – Liquid phase

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08/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Process flow – Liquid phase

• Feed dryer
• HE (to preheat feed to 60 – 100 C)
• Catalyst scrubber
• Agitator reactor (Feed : mixture of HC, H2 and HCl)
• Wash column: to wash effluents with water/alcohol to
remove catalyst
• Accumulator (Flash drum)
• Stripper (to remove HCl)

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08/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Commercial technologies

• Hysomer process (Union carbide/Shell)

• Pentanes and hexanes as primary feed, Metal deposited on zeolite
used as catalyst, Can handle feed with 35 – 50 ppm of sulfur or water
• Catalyst is regenerable
• Operating conditions
• Penex (UOP)
• Pentanes or hexanes isomerized over Pt containing catalyst
• Operating conditions
• Isomate (non-regenerative isomerization process)
• ISOFIN (KBR)
• Butamer (UOP) 23

08/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Polymerization

• Produces polymer gasoline

• Convert off-gases from thermal crackers
• Thermal (not effective) or catalytic (industrially operated)
units
• Catalyst: Copper pyrophosphate on charcoal, sulfuric
acid, phosphoric acid
• Operating conditions: Temp < 200 C; P: 10 – 80 atm
• Rx: Exothermic (225 to 300 Kcal/kg of polymer formed)
• Process
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08/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus

 Polymerization

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08/11/2020 Amol Deshpande BITS Pilani, K K Birla Goa Campus