Catalytic Reforming and BTX Aromatics Production

This group covers the fundamental principles of catalytic reforming, the sources of aromatics,
and the initial recovery and isolation of BTX (benzene, toluene, xylenes) from reformate.

a) Definition of Catalytic Reforming:

Catalytic reforming is a refining process that converts low-octane naphtha into high-octane
reformate, which is a gasoline blending component. The process also produces significant
quantities of aromatic hydrocarbons (benzene, toluene, xylenes) as by-products. Reforming
involves the rearrangement of hydrocarbon molecules in the presence of a catalyst and
hydrogen.

b) Principle of Catalytic Reforming for Aromatics Production:

The process operates on the principle of converting naphthenes (cycloalkanes) and paraffins
into aromatics through several reactions:

• Dehydrogenation of Naphthenes: Cyclohexane derivatives are dehydrogenated to

form benzene, toluene, and xylenes.
• Dehydrocyclization of Paraffins: Straight-chain paraffins are cyclized and
dehydrogenated to form aromatics.
• Isomerization: Normal paraffins and naphthenes are converted to branched isomers.
• Hydrocracking: Small amounts of cracking occur, producing lighter hydrocarbons.

c) Catalyst Used in Reforming Process:

The catalyst is typically bimetallic containing:

• Platinum (Pt) as the active metal for dehydrogenation

• Rhenium (Re) or Tin (Sn) as promoters to improve stability and selectivity
• Supported on chlorinated alumina (Al₂O₃)

d) Objectives of Aromatics Production:

1. High-Octane Gasoline Blending: Reformate has high octane number.

 2. Petrochemical Feedstock: Production of benzene, toluene, and xylenes for
downstream chemical industries.
3. Hydrogen Generation: The process produces hydrogen as a valuable by-product for
other refining processes.

e) Sources of Aromatics in Petroleum Refining:

Source Description

Catalytic Reforming Primary source of BTX aromatics from naphtha

Steam Cracking Pyrolysis gasoline from ethylene plants contains aromatics

Coke Oven Light Oil From coal carbonization (historical source)

Toluene Disproportionation Conversion of toluene to benzene and xylenes

f) Need for Isolation of Aromatics from Reformate:

Reformate is a complex mixture containing aromatics (30–70%), paraffins, and naphthenes.
Aromatics must be isolated because:

• They are valuable petrochemical feedstocks (benzene for styrene, xylenes for
polyester)
• They have high octane but are regulated in gasoline due to toxicity and emissions
concerns
• Separation allows individual aromatics to be purified for specific applications

g) Recovery and Isolation of BTX Aromatics from Reformate:

The separation sequence involves the following steps:

Fractional Distillation (Prefractionation):

Reformate is first distilled to separate it into narrow boiling fractions:

• Light Reformate: Contains benzene and lighter components

• Toluene Cut: Contains toluene (boiling point 110.6°C)
 • Xylene Cut: Contains C₈ aromatics (xylenes and ethylbenzene, boiling range 135–
145°C)
• Heavy Reformate: Contains C₉+ aromatics

Solvent Extraction for BTX Separation:

Solvent extraction is used to separate aromatics from non-aromatics (paraffins and
naphthenes) in the light reformate and toluene cuts. The process uses a selective solvent that
dissolves aromatics but not non-aromatics.

Solvent Used: Sulfolane (tetrahydrothiophene dioxide) is the most common solvent for BTX
extraction. Other solvents include N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO),
and dimethylformamide (DMF).

Advantages of Solvent Extraction Method:

1. High selectivity for aromatics (up to 99.9% recovery)

2. Energy efficient compared to extractive distillation for BTX separation
3. Continuous operation with solvent recycle
4. Produces high-purity aromatics suitable for downstream processing

h) Extractive Distillation for Aromatics Separation:

Extractive distillation is an alternative separation method where a solvent is added to alter
the relative volatilities of components with close boiling points. For aromatics, a high-boiling
solvent is added to the distillation column, which preferentially interacts with aromatics,
allowing non-aromatics to be taken overhead.

i) Comparison of Solvent Extraction and Extractive Distillation Methods:

Aspect Solvent Extraction Extractive Distillation

Liquid-liquid extraction based on Distillation with solvent altering

Principle
solubility volatility

Solvent Sulfolane, NMP Sulfolane, NMP (higher boiling)

Aspect Solvent Extraction Extractive Distillation

Aromatics extracted into solvent

Product Aromatics recovered as bottoms
phase

Energy Higher (requires solvent

Moderate
Consumption regeneration)

Application BTX from reformate Narrow-cut aromatics separation

j) Operating Conditions for Catalytic Reforming:

Parameter Typical Range

Temperature 480–550°C

10–35 bar (moderate pressure to suppress coke

Pressure
formation)

Hydrogen-to-Hydrocarbon Ratio 2–10 (molar)

Space Velocity 1–3 h⁻¹ (LHSV)

Catalyst Pt-Re/Al₂O₃ or Pt-Sn/Al₂O₃

k) Complete Process of Aromatics Production by Catalytic Reforming:

The process sequence is as follows:

Feed Pretreatment: Naphtha feedstock is hydrotreated to remove sulfur, nitrogen, and

metals that poison the reforming catalyst. This is typically done in a hydrotreater unit using
cobalt-molybdenum or nickel-molybdenum catalysts.

Reforming Reactors: The pretreated naphtha is mixed with hydrogen and passed through a
series of fixed-bed reactors (typically 3–4 in series) containing the bimetallic catalyst. The
reactions are endothermic, so interstage heating is required between reactors.
Product Separation: The reformate effluent is cooled, and hydrogen is separated and
recycled. The liquid reformate is sent to a stabilizer column to remove light ends (C₄ and
lighter).

BTX Recovery: The stabilized reformate undergoes distillation and solvent extraction to
recover benzene, toluene, and mixed xylenes as described above.

l) Economic Importance of Aromatics in Petrochemical Industry:

Aromatics (benzene, toluene, xylenes) are among the highest-volume petrochemicals.
Benzene is the precursor to styrene, phenol, and nylon intermediates. Toluene is used as a
solvent and for producing benzene and xylenes. Xylenes (particularly p-xylene) are the
foundation of the polyester industry via terephthalic acid. The BTX complex represents a
multi-billion-dollar global market.

m) Environmental Concerns in Aromatics Production:

Concern Description

Benzene is a known human carcinogen; fugitive emissions must be

Benzene Emissions
controlled

Energy
Reforming and separation processes are energy-intensive
Consumption

Hydrogen Sulfide Formed during hydrotreating; requires sulfur recovery

Spent reforming catalysts contain platinum and other metals requiring

Catalyst Disposal
recovery

VOC Emissions Volatile organic compounds from storage and handling

C₈ Aromatics – Xylene Isomers and Separation

This group covers the specific challenges associated with C₈ aromatics, including the
separation of xylene isomers, isomerization processes, and adsorptive separation techniques.

a) Definition of C₈ Aromatics:
C₈ aromatics are aromatic hydrocarbons containing eight carbon atoms. They are derived
primarily from catalytic reforming and steam cracking (pyrolysis gasoline).

b) Isomers Present in C₈ Aromatics:

Boiling Melting
Isomer Importance
Point Point

Highest demand; used for

p-Xylene (para-xylene) 138.4°C 13.3°C
terephthalic acid

m-Xylene (meta-
139.1°C -47.9°C Used for isophthalic acid
xylene)

o-Xylene (ortho-
144.4°C -25.2°C Used for phthalic anhydride
xylene)

Ethylbenzene 136.2°C -95.0°C Used for styrene production

c) Difficulty in Separation of C₈ Isomers:

The boiling points of the four C₈ isomers are extremely close (spread of only 8°C). This makes
fractional distillation impractical for separating individual isomers because it would require
thousands of theoretical plates and very high reflux ratios, making it economically unfeasible.
The most challenging separation is between p-xylene and m-xylene, which differ by only
0.7°C.

d) Separation of C₈ Aromatics by Fractional Distillation:

Fractional distillation can only separate o-xylene (boiling point 144.4°C) from the other three
isomers. The mixture of p-xylene, m-xylene, and ethylbenzene (boiling range 136–139°C)
cannot be effectively separated by distillation alone and requires advanced techniques.
e) Adsorptive Separation Technique (Parex Process):
The Parex process (developed by UOP) is the dominant method for separating p-xylene from
mixed xylenes. It uses a simulated moving bed (SMB) adsorption system with a solid
adsorbent.

Principle: A molecular sieve adsorbent (typically zeolite-based) selectively adsorbs p-xylene

due to its molecular shape and size. The adsorbent has pore dimensions that preferentially
admit the para-isomer (which has a smaller molecular diameter) over the meta and ortho
isomers and ethylbenzene.

Process: The mixed xylenes are passed through a bed of adsorbent. p-Xylene is adsorbed,
while the other isomers pass through. A desorbent (such as p-diethylbenzene or toluene) is
then used to desorb the p-xylene. The process operates continuously with multiple beds in a
simulated moving bed configuration.

f) Isomerization in C₈ Aromatics Processing:

Isomerization is used to convert the less valuable m-xylene and ethylbenzene into additional
p-xylene. The process involves passing the xylene mixture (after p-xylene removal) over a
catalyst that equilibrates the isomers to the thermodynamic equilibrium composition.

Chemical Reaction:

• m-Xylene ⇌ p-Xylene
• o-Xylene ⇌ p-Xylene
• Ethylbenzene → Xylenes (by isomerization or disproportionation)

Catalyst: Acidic zeolite catalysts (such as ZSM-5) with metal components (platinum) for
hydrogenation-dehydrogenation functions.

g) Operating Conditions for Xylene Isomerization:

Parameter Range

Temperature 350–450°C
Parameter Range

Pressure 10–20 bar

Catalyst Zeolite (ZSM-5) with Pt or other metals

Hydrogen Added to reduce coke formation

h) Role of Adsorption in Xylene Separation:

Adsorption leverages the difference in molecular size and shape between xylene isomers.
Para-xylene has a smaller kinetic diameter (approximately 5.8 Å) compared to meta and
ortho isomers, allowing it to enter the pores of specific zeolites (such as BaX or BaKX)
selectively. This shape-selective adsorption is the basis for commercial p-xylene recovery.

i) Solvent Extraction vs. Extractive Distillation for Aromatics:

Aspect Solvent Extraction Extractive Distillation

Liquid-liquid extraction based on

Principle Distillation with selective solvent
relative solubility

Solvent Sulfolane, NMP, DMSO Sulfolane, NMP

BTX separation from Benzene/toluene separation from

Application
paraffins/naphthenes close-boiling non-aromatics

Aromatics
High (>99.9%) High (>99.5%)
Purity

j) Economic and Environmental Aspects of Aromatics Production:

• Economic: p-Xylene is the largest-volume xylene isomer due to its use in polyester
production. Global p-xylene demand exceeds 50 million tons annually. The economic
viability of aromatics complexes depends on efficient separation and isomerization to
maximize p-xylene yield.
 • Environmental: Aromatics production involves significant energy consumption and
CO₂ emissions. Benzene emissions require strict controls due to carcinogenicity.
Modern plants use closed-loop systems, vapor recovery, and catalytic incinerators to
minimize emissions.

Benzene Derivatives – Ethylbenzene and Styrene

This group covers the production of ethylbenzene from benzene and ethylene, followed by
dehydrogenation to styrene, and the polymerization of styrene to polystyrene.

a) Definition of Benzene Derivatives:

Benzene derivatives are chemical compounds produced from benzene through substitution
reactions. Major benzene derivatives include ethylbenzene, cumene (isopropylbenzene),
phenol, styrene, and cyclohexane.

b) Principle of Ethylbenzene Manufacture by Alkylation:

Ethylbenzene is produced by the alkylation of benzene with ethylene in the presence of a
catalyst. The reaction is a Friedel-Crafts alkylation.

Chemical Reaction:
C₆H₆ + CH₂=CH₂ → C₆H₅–CH₂CH₃

c) Catalysts Used in Ethylbenzene Manufacture:

Catalyst Type Description

Aluminum Chloride
Traditional catalyst; homogeneous liquid-phase process
(AlCl₃)

Modern solid-acid catalyst; vapor-phase or liquid-phase process (e.g., Mobil-Badger

Zeolite (ZSM-5, Beta)
Lummus/UOP)
d) Alkylation of Benzene:
Alkylation is the introduction of an alkyl group (such as ethyl or isopropyl) onto an aromatic
ring. For ethylbenzene production, benzene reacts with ethylene in the presence of an acid
catalyst. The reaction is exothermic and requires careful temperature control.

e) Raw Materials Required for Ethylbenzene Production:

1. Benzene (from catalytic reforming or hydrodealkylation)

2. Ethylene (from steam cracking)

f) Operating Conditions for Ethylbenzene Production:

Vapor-Phase Process Liquid-Phase Process

Parameter
(Zeolite) (Zeolite)

Temperature 350–450°C 200–300°C

Pressure 10–30 bar 30–50 bar

Benzene/Ethylene Ratio 5–10 (molar) 3–5 (molar)

g) Friedel–Crafts Alkylation:
Friedel-Crafts alkylation is a classic organic reaction where an alkyl halide or alkene reacts
with an aromatic compound in the presence of a Lewis acid catalyst (such as AlCl₃) or a solid
acid catalyst. In ethylbenzene production, ethylene acts as the alkylating agent, and the
catalyst generates a carbocation intermediate that attacks the benzene ring.

h) Reaction Mechanism of Alkylation of Benzene:

1. Activation: Ethylene is protonated by the acid catalyst to form an ethyl carbocation.

2. Electrophilic Attack: The ethyl carbocation attacks the benzene ring, forming a sigma
complex (arenium ion).
3. Deprotonation: Loss of a proton regenerates the catalyst and yields ethylbenzene.
4. Side Reactions: Polyalkylation (formation of diethylbenzene and triethylbenzene)
occurs, requiring transalkylation to convert them back to ethylbenzene.
i) Comparison of Liquid Phase and Vapor Phase Alkylation Processes:

Aspect Liquid Phase Vapor Phase

Catalyst Zeolite (Beta) Zeolite (ZSM-5)

Temperature 200–300°C 350–450°C

Pressure 30–50 bar 10–30 bar

Benzene/Ethylene Ratio Lower (3–5) Higher (5–10)

Energy Consumption Lower (no vaporization) Higher

Selectivity Higher (less polyalkylation) Moderate

j) Separation and Purification of Ethylbenzene from Reaction Mixture:

The alkylation reactor effluent contains ethylbenzene, unreacted benzene, polyalkylated
benzenes (diethylbenzene, triethylbenzene), and light ends. The purification sequence is:

1. Benzene Recovery: Unreacted benzene is recovered by distillation and recycled.

2. Ethylbenzene Distillation: Ethylbenzene is separated from heavier components.
3. Polyalkylate Recovery: Diethylbenzene and triethylbenzene are recovered and sent to
a transalkylation reactor where they react with additional benzene to produce
ethylbenzene.
4. Heavy Ends Removal: High-boiling impurities are removed.

k) Principle of Styrene Manufacture from Ethylbenzene:

Styrene is produced by the catalytic dehydrogenation of ethylbenzene. The reaction removes
two hydrogen atoms from the ethyl group, forming a vinyl group.

Chemical Reaction:
C₆H₅–CH₂CH₃ → C₆H₅–CH=CH₂ + H₂ (endothermic)

l) Dehydrogenation Process:
Dehydrogenation is the removal of hydrogen from a molecule. In styrene production,
ethylbenzene is passed over a catalyst at high temperature in the presence of superheated
steam. The steam serves multiple functions:

• Provides heat for the endothermic reaction

• Lowers the partial pressure of hydrogen, shifting equilibrium toward styrene
• Suppresses coke formation
• Reduces catalyst deactivation

m) Catalyst Used in Styrene Manufacture:

The catalyst is iron oxide (Fe₂O₃) promoted with:

• Potassium carbonate (K₂CO₃) – enhances activity and selectivity

• Chromium oxide (Cr₂O₃) – improves stability
• Cerium oxide (CeO₂) or other promoters – further enhance performance

n) Operating Conditions for Styrene Production:

Parameter Range

Temperature 600–650°C

Pressure Near atmospheric (0.5–1.5 bar)

Steam-to-Ethylbenzene Ratio 8–12 (molar)

Catalyst Fe₂O₃/K₂O/Cr₂O₃

o) By-Products Formed During Styrene Manufacture:

By-Product Source Use or Disposal

Toluene Side reactions Recovered or recycled

Benzene Side reactions Recovered or recycled

Hydrogen Main reaction Fuel gas or used in other processes

By-Product Source Use or Disposal

Coke Catalyst deactivation Burned off during regeneration

Heavy Ends Polymerization products Fuel or disposal

p) Purification Steps Involved in Styrene Production:

1. Quenching: The reactor effluent is quenched with water to condense organic

products.
2. Decantation: Separation of organic and aqueous phases.
3. Benzene/Toluene Recovery: Light ends are distilled and recycled.
4. Ethylbenzene Recovery: Unreacted ethylbenzene is recovered and recycled.
5. Styrene Distillation: Styrene is purified by distillation under vacuum (to prevent
thermal polymerization). Polymerization inhibitors are added.
6. Residue Removal: Heavy ends and polymers are removed.

q) Polymerization of Styrene:
Styrene undergoes addition polymerization to form polystyrene (PS). The polymerization can
be carried out by several methods:

• Bulk Polymerization: For crystal polystyrene

• Suspension Polymerization: For expandable polystyrene (EPS)
• Emulsion Polymerization: For latexes

Chemical Reaction:
n C₆H₅–CH=CH₂ → [–CH(C₆H₅)–CH₂–]ₙ

r) Properties of Styrene:

Property Description

Physical
Colorless liquid at room temperature
State
Property Description

Boiling
145°C
Point

Reactivity Highly reactive; polymerizes readily in the presence of heat, light, or peroxides

Requires addition of polymerization inhibitors (e.g., tert-butylcatechol) during

Stabilization
storage and transport

s) Industrial Applications of Ethylbenzene and Styrene:

Product Application

Intermediate for styrene production (over 99% of ethylbenzene is used for

Ethylbenzene
styrene)

Polystyrene (packaging, disposable cups, insulation), ABS resins (automotive,

Styrene appliances), SBR rubber (tires), unsaturated polyester resins (boat hulls,
automotive parts)

t) Environmental and Safety Aspects in Benzene Derivative Production:

Concern Mitigation

Enclosed systems; continuous monitoring; personal protective

Benzene Toxicity
equipment

Flammability Explosion-proof electrical equipment; inert gas purging

Ethylene Oxide Used in some processes; highly reactive and toxic

Polymerization Styrene and ethylbenzene can polymerize; inhibitors added; temperature

Risk control
Concern Mitigation

Emissions Vapor recovery systems; thermal oxidizers

u) Economic Importance of Benzene Derivatives:

Benzene derivatives, particularly ethylbenzene/styrene, represent one of the largest-volume
petrochemical chains. Polystyrene is one of the top five commodity plastics. The styrene
chain (benzene → ethylbenzene → styrene → polystyrene/ABS/SBR) is a multi-billion-dollar
industry globally.

Xylene Derivatives – Phthalic Anhydride, Terephthalic Acid, and DMT

This group covers the production of phthalic anhydride from o-xylene, terephthalic acid (TPA)
and dimethyl terephthalate (DMT) from p-xylene, and their industrial applications.

a) Definition of Xylene Isomers:

Xylene isomers are dimethylbenzenes with the formula C₆H₄(CH₃)₂. The three isomers (ortho,
meta, para) differ in the positions of the methyl groups on the benzene ring.

b) Principle of Phthalic Anhydride Manufacture from o-Xylene:

Phthalic anhydride is produced by the catalytic vapor-phase oxidation of o-xylene (or
naphthalene). The reaction involves the oxidation of both methyl groups to carboxylic acids
followed by dehydration to form the anhydride.

Chemical Reaction:
o-C₆H₄(CH₃)₂ + 3O₂ → C₆H₄(CO)₂O + 3H₂O

c) Catalyst Used in Phthalic Anhydride Manufacture:

The catalyst is vanadium pentoxide (V₂O₅) supported on titanium dioxide (TiO₂) with
promoters such as cesium or phosphorus. The catalyst is typically in a fixed-bed or fluidized-
bed configuration.
d) Operating Conditions for Phthalic Anhydride Production:

Parameter Range

Temperature 350–400°C

Pressure Near atmospheric to 2 bar

Catalyst V₂O₅/TiO₂ (promoted)

Air-to-o-Xylene Ratio High (excess air to maintain safe operation)

e) Reaction Mechanism of Oxidation of o-Xylene:

The oxidation proceeds through a series of intermediates:

1. o-Xylene is oxidized to o-tolualdehyde

2. Further oxidation to o-toluic acid
3. Oxidation to phthalic acid
4. Dehydration to phthalic anhydride

The reaction is highly exothermic and requires careful temperature control to prevent
complete combustion to CO₂ and water.

f) Separation and Purification in Phthalic Anhydride Production:

1. Condensation: The reactor effluent is cooled, and phthalic anhydride is condensed as

a solid (desublimation) or absorbed.
2. Distillation: Crude phthalic anhydride is distilled under vacuum to remove impurities.
3. Refining: Further purification by distillation or crystallization yields high-purity
phthalic anhydride.

g) Properties and Uses of Phthalic Anhydride:

Property Description

Physical State White solid (melting point 131°C)

Reactivity Reacts with alcohols to form phthalate esters

Industrial Plasticizers (phthalate esters), alkyd resins, polyester resins, dye

Applications intermediates

h) Principle of Terephthalic Acid Manufacture from p-Xylene:

Terephthalic acid (TPA) is produced by the catalytic liquid-phase oxidation of p-xylene with air
or oxygen. The reaction oxidizes both methyl groups to carboxylic acids.

Chemical Reaction:
p-C₆H₄(CH₃)₂ + 3O₂ → p-C₆H₄(COOH)₂ + 2H₂O

i) Catalyst Used in Terephthalic Acid Production:

The catalyst system is a cobalt-manganese-bromide (Co-Mn-Br) system, typically with a
bromide promoter such as hydrogen bromide or tetrabromoethane. This is known as
the Amoco process (now BP/INVISTA).

j) Operating Conditions for TPA Production:

Parameter Range

Temperature 150–250°C

Pressure 10–20 bar (to maintain liquid phase)

Catalyst Co/Mn/Br (homogeneous)

Solvent Acetic acid

Air Excess oxygen for complete conversion

k) Reaction Mechanism of Oxidation of p-Xylene:
The oxidation proceeds through a free radical mechanism:

1. Initiation by Co³⁺ or Br• radicals

2. p-Xylene is oxidized to p-tolualdehyde
3. Further oxidation to p-toluic acid
4. Final oxidation to terephthalic acid

The bromide promoter accelerates the reaction and improves selectivity.

l) By-Products Formed During Oxidation of p-Xylene:

By-Product Description

4-Carboxybenzaldehyde (4- Intermediate; must be removed to very low levels (ppm) for
CBA) polymer-grade TPA

p-Toluic Acid Intermediate; recycled

Acetic Acid Solvent; recovered and recycled

Methyl Acetate By-product; recovered or used as fuel

CO₂ Complete combustion product

m) Purification Steps Involved in TPA Production:

Crystallization: Crude TPA is crystallized from the reaction mixture.

Purification (Hydrogenation): Crude TPA contains 4-CBA and other impurities that discolor
polyester. Purification involves dissolving crude TPA in water at high temperature and
pressure, then hydrogenating over a palladium-on-carbon catalyst. This converts 4-CBA to p-
toluic acid (which is more easily separated) and reduces color-forming impurities.

Separation: Purified TPA is crystallized, filtered, washed, and dried to obtain polymer-grade
TPA (>99.9% purity, 4-CBA <25 ppm).
n) Principle of Dimethyl Terephthalate (DMT) Manufacture:
DMT is the dimethyl ester of terephthalic acid. It can be produced by two routes:

1. Esterification of TPA: TPA reacts with methanol to form DMT.

2. Oxidation of p-Xylene followed by Esterification: The Witten process (Hercules-
Dynamit Nobel) oxidizes p-xylene to p-toluic acid, which is esterified to methyl p-
toluate, then further oxidized and re-esterified to DMT.

o) Chemical Reactions for DMT Formation:

From TPA (Esterification):
C₆H₄(COOH)₂ + 2CH₃OH → C₆H₄(COOCH₃)₂ + 2H₂O

From p-Xylene (Witten Process):

• p-C₆H₄(CH₃)₂ + O₂ → p-CH₃–C₆H₄–COOH (p-toluic acid)

• p-CH₃–C₆H₄–COOH + CH₃OH → p-CH₃–C₆H₄–COOCH₃ (methyl p-toluate)
• p-CH₃–C₆H₄–COOCH₃ + O₂ → p-CH₃OOC–C₆H₄–COOCH₃ (DMT)

p) Comparison of TPA and DMT Production Processes:

Aspect TPA (Amoco Process) DMT (Witten Process)

Product Terephthalic acid Dimethyl terephthalate

Solvent Acetic acid No solvent or p-xylene

Catalyst Co/Mn/Br Co/Mn (sometimes with Br)

Purification Hydrogenation + crystallization Distillation + crystallization

Esterification Not required (TPA is final) Required (methanol)

Energy Consumption Moderate Higher (methanol recovery)

q) Manufacture of DMT by Esterification and Transesterification:

 • Esterification: TPA is reacted with excess methanol in the presence of an acid catalyst
(such as sulfuric acid or p-toluenesulfonic acid) to form DMT and water.
• Transesterification: DMT can also be produced by transesterification of dimethyl
terephthalate with other alcohols, but this is not a primary production method.

r) Separation and Purification Steps in DMT Production:

1. Methanol Recovery: Excess methanol is recovered by distillation.

2. Distillation: Crude DMT is distilled to remove high-boiling and low-boiling impurities.
3. Crystallization: DMT is crystallized to obtain high-purity product.
4. Finishing: Final product is flaked or shipped molten.

s) Industrial Applications of TPA and DMT:

Product Application

Terephthalic Acid Polyethylene terephthalate (PET) for fibers, bottles, films;

(TPA) polybutylene terephthalate (PBT) for engineering plastics

Dimethyl PET production (particularly for polyester fibers); also used for
Terephthalate (DMT) polybutylene terephthalate and other polyesters

t) Role of Cobalt-Manganese Catalyst System in TPA Production:

The Co-Mn-Br catalyst system is a synergistic homogeneous catalyst:

• Cobalt provides the primary oxidation activity

• Manganese enhances activity and selectivity
• Bromide acts as a promoter, generating bromine radicals that accelerate the
oxidation and suppress side reactions

u) Quality Control Measures in TPA Production:

Key quality parameters for polymer-grade TPA:

• Purity: >99.9%
• 4-CBA Content: <25 ppm (critical for polyester polymerization)
 • Color: Low b* value (yellowness)
• Ash Content: <10 ppm
• Water Content: <0.5%

v) Economic Importance of Xylene Derivatives in Polyester Industry:

p-Xylene and its derivatives (TPA and DMT) are the foundation of the polyester industry.
Global PET production exceeds 80 million tons annually, used in:

• Polyester Fibers: The largest use, for textiles and apparel

• PET Bottles: Beverage and food packaging
• PET Films: Packaging, photographic, and electrical applications

The p-xylene → TPA → PET value chain represents one of the largest-volume petrochemical
value chains globally.

w) Environmental and Safety Aspects in Xylene Derivative Plants:

Concern Mitigation

p-Xylene
Flammable liquid; proper storage and handling; vapor recovery
Flammability

Acetic Acid Corrosive; requires stainless steel equipment

Heavy metals; requires wastewater treatment and spent catalyst

Cobalt/Manganese
disposal/recovery

Bromide
Corrosive and toxic; proper handling and emissions control
Compounds

TPA Dust Respiratory hazard; dust collection systems

Wastewater Contains acetic acid, methanol, and catalyst metals; requires treatment

x) Challenges in Oxidation Reactions of Xylene Isomers:

 1. Selectivity: Competing complete combustion to CO₂ reduces yield.
2. Heat Removal: Highly exothermic reactions require effective cooling.
3. Corrosion: Bromide and acetic acid are corrosive, requiring specialized materials.
4. Impurity Control: 4-CBA removal requires additional purification steps.
5. Catalyst Recovery: Homogeneous catalysts (Co, Mn) must be recovered from waste
streams.

Hydrotreating (Hydrodesulfurization and Hydrotreating)

This group covers hydrotreating processes used to remove impurities (sulfur, nitrogen,
metals) from petroleum fractions.

a) Definition of Hydrotreating:
Hydrotreating is a refining process that uses hydrogen to remove undesirable impurities
(sulfur, nitrogen, oxygen, metals, and olefins) from petroleum fractions. It improves product
quality and prepares feedstocks for downstream processes like catalytic reforming and
hydrocracking.

b) Objective of Hydrotreating Process:

1. Sulfur Removal: Reduce sulfur content to meet environmental regulations (e.g., ultra-
low sulfur diesel).
2. Nitrogen Removal: Remove nitrogen compounds that poison downstream catalysts.
3. Metal Removal: Remove nickel, vanadium, and other metals that deactivate catalysts.
4. Olefin Saturation: Saturate olefins to improve stability.
5. Color and Odor Improvement: Remove compounds that cause undesirable color and
odor.

c) Hydrodesulfurization (HDS):
Hydrodesulfurization is a specific type of hydrotreating focused on sulfur removal. The
reaction converts organic sulfur compounds to hydrogen sulfide (H₂S), which is then removed
and converted to elemental sulfur in a Claus unit.

Reaction Involved in Sulfur Removal:

R–SH (thiol) + H₂ → R–H + H₂S
R–S–R' (sulfide) + 2H₂ → R–H + R'–H + H₂S

d) Catalyst Used in Hydrotreating:

The catalysts are typically cobalt-molybdenum (Co-Mo) or nickel-molybdenum (Ni-
Mo) sulfides supported on alumina (Al₂O₃).

• Co-Mo/Al₂O₃: Preferred for hydrodesulfurization

• Ni-Mo/Al₂O₃: Preferred for hydrodenitrogenation (more active for nitrogen removal)

e) Operating Conditions for Hydrotreating:

Parameter Range

Temperature 300–400°C

Pressure 20–100 bar (higher for heavier feeds)

Hydrogen-to-Oil Ratio 50–300 Nm³/m³

Space Velocity 1–5 h⁻¹ (LHSV)

f) Complete Process of Hydrotreating:

The hydrotreating process follows this sequence:

Feed Preheating: The feedstock (naphtha, kerosene, diesel, or VGO) is preheated and mixed
with hydrogen-rich recycle gas.

Reactor Section: The mixture passes through a fixed-bed reactor containing the Co-Mo or Ni-
Mo catalyst. Sulfur, nitrogen, and other impurities react with hydrogen to form H₂S, NH₃, and
saturated hydrocarbons.
Product Separation: The reactor effluent is cooled and sent to a high-pressure separator.
Hydrogen-rich gas is separated and recycled.

Fractionation: The liquid product is sent to a stripper or fractionator to remove H₂S, NH₃, and
light ends. The treated product is recovered.

g) Environmental Benefits of Hydrotreating:

1. Reduced SOₓ Emissions: Removal of sulfur from fuels reduces sulfur dioxide emissions
from combustion.
2. Lower Particulate Matter: Reduced sulfur content in diesel decreases particulate
emissions.
3. Catalyst Protection: Provides clean feed for downstream processes like catalytic
reforming and hydrocracking.

h) Advantages and Limitations of Hydrotreating:

Advantages Limitations

Produces clean, high-quality fuels High hydrogen consumption (cost)

Extends catalyst life in downstream units Capital-intensive (high pressure)

Reduces environmental pollution Requires hydrogen availability

Improves product stability Catalyst disposal (spent catalyst contains metals)

Hydrocracking

This group covers the hydrocracking process, which combines cracking with hydrogenation to
produce high-quality products.
a) Definition of Hydrocracking:
Hydrocracking is a refining process that uses hydrogen and a catalyst to break down heavy
hydrocarbon molecules (vacuum gas oil, residues) into lighter, more valuable products such
as naphtha, kerosene, and diesel. The process combines catalytic cracking with
hydrogenation.

b) Principle of Hydrocracking:
Hydrocracking involves the simultaneous cracking of large hydrocarbon molecules and
hydrogenation of the resulting fragments. The hydrogenation step saturates olefins and
removes sulfur, nitrogen, and metals, producing stable, high-quality products.

c) Catalysts Used in Hydrocracking:

Hydrocracking uses bifunctional catalysts that provide both cracking and hydrogenation
functions:

• Cracking Function: Acidic support such as amorphous silica-alumina or zeolite (Y-

zeolite, ZSM-5)
• Hydrogenation Function: Noble metals (platinum, palladium) or base metals (nickel-
tungsten, nickel-molybdenum)

d) Operating Conditions for Hydrocracking:

Parameter Range

Temperature 300–450°C

Pressure 70–200 bar (very high)

Hydrogen-to-Oil Ratio 500–2000 Nm³/m³

Space Velocity 0.5–2 h⁻¹ (LHSV)

e) Products Obtained from Hydrocracking:

Product Description

LPG Propane, butanes

Light Naphtha High-octane gasoline blending component

Heavy Naphtha Feedstock for catalytic reforming

Kerosene Jet fuel

Diesel High-cetane diesel fuel

Unconverted Oil Recycled or sent to other units

f) Reaction Mechanism in Hydrocracking:

The mechanism involves several steps:

1. Cracking (Acid Function): Large hydrocarbons are cracked on acid sites via carbenium
ion mechanism, producing olefins and smaller carbocations.
2. Hydrogenation (Metal Function): Olefins are hydrogenated to saturated
hydrocarbons.
3. Isomerization: Branched hydrocarbons are formed, improving product quality (octane
for naphtha, cold flow for diesel).
4. Heteroatom Removal: Sulfur, nitrogen, and metals are removed via hydrotreating
reactions.

g) Role of Hydrogen in Hydrocracking:

Hydrogen serves multiple critical functions:

• Suppresses Coke Formation: Prevents catalyst deactivation by saturating olefins

• Provides Heat of Reaction: Hydrogenation reactions are exothermic, providing heat
for cracking
• Improves Product Quality: Produces stable, saturated products
• Removes Impurities: Converts sulfur and nitrogen to H₂S and NH₃
h) Comparison of Hydrocracking and Catalytic Cracking (FCC):

FCC (Fluid Catalytic

Aspect Hydrocracking
Cracking)

Hydrogen Requires hydrogen (consumes H₂) No hydrogen consumption

Pressure Very high (70–200 bar) Moderate (1–5 bar)

Catalyst Bifunctional (acid + hydrogenation) Acidic zeolite (no metal)

Higher (saturated, low sulfur, high Lower (contains olefins,

Product Quality
cetane) sulfur)

Feedstock Heavier, poorer quality VGO, residues

Conversion Complete conversion possible Partial conversion with recycle

Capital Cost Higher Lower

i) Differences Between Hydrocracking and Visbreaking:

Aspect Hydrocracking Visbreaking

Objective Produce high-quality light products Reduce viscosity of residues

Hydrogen Requires hydrogen No hydrogen

Conversion High (50–100%) Low (10–20%)

Product Quality High (saturated, stable) Lower (contains olefins)

High pressure, moderate High temperature, low

Operating Severity
temperature pressure

j) By-Products Formed in Hydrocracking:

 • Hydrogen Sulfide (H₂S): From sulfur removal
• Ammonia (NH₃): From nitrogen removal
• Light Gases (C₁–C₄): From over-cracking
• Coke: Minimal due to hydrogenation

k) Advantages and Limitations of Hydrocracking:

Advantages Limitations

High flexibility in product slate Very high capital investment

Produces high-quality products (low sulfur, high cetane) High hydrogen consumption

Can process poor-quality feedstocks Sensitive to feedstock contaminants

High conversion (up to 100%) Complex process control

Group 7: Visbreaking (Thermal Cracking of Residues)

This group covers the visbreaking process, a mild thermal cracking process used to reduce
viscosity of heavy residues.

a) Definition of Visbreaking:
Visbreaking (viscosity breaking) is a mild thermal cracking process used to reduce the
viscosity of atmospheric or vacuum residues (heavy fuel oil). The process produces lighter
products (gas, naphtha, gas oil) and a reduced-viscosity residue suitable for fuel oil blending.

b) Principle of Visbreaking:
Visbreaking involves the thermal cracking of heavy residues at moderate temperatures (450–
500°C) and low pressures. The process breaks large asphaltene and resin molecules into
smaller molecules, reducing viscosity and pour point.

c) Feedstock Used in Visbreaking:

 • Atmospheric Residue (AR)
• Vacuum Residue (VR)
• Heavy fuel oil components

d) Operating Conditions for Visbreaking:

Parameter Range

Temperature 450–500°C

Pressure 5–20 bar

Residence Time 1–5 minutes (coil type) or 10–30 minutes (soaker type)

e) Complete Visbreaking Process:

The visbreaking process follows this sequence:

Feed Heating: The residue feedstock is heated in a furnace to the required cracking
temperature.

Reaction Section: Two main configurations exist:

• Coil Visbreaking: Cracking occurs in the furnace tubes with short residence time.
• Soaker Visbreaking: Feed is heated to lower temperature and then held in a soaking
drum for longer residence time, reducing furnace coking.

Quenching: The reactor effluent is rapidly quenched (with cold gas oil or water) to stop the
cracking reaction.

Fractionation: The quenched effluent is sent to a fractionator where gas, naphtha, gas oil,
and visbroken residue are separated.

f) Product Distribution in Visbreaking Process:

Product Typical Yield (%)

Gas (C₁–C₄) 5–15

Naphtha (C₅–165°C) 5–15

Gas Oil (165–350°C) 10–25

Visbroken Residue 50–70

g) Advantages of Visbreaking:

1. Reduces Viscosity: Makes heavy residues suitable for fuel oil blending.
2. Low Capital Cost: Simple process compared to hydrocracking.
3. Produces Additional Lighter Products: Naphtha and gas oil can be upgraded in other
units.
4. Flexible Operation: Can handle various residue types.

h) Limitations of Visbreaking Process:

1. Limited Conversion: Only 10–20% conversion to lighter products.

2. Product Instability: Visbroken residue contains olefins and can form sediments
(requires stabilization).
3. Coke Formation: Furnace tubes can coke, requiring periodic decoking.
4. No Hydrogen: Does not improve product quality in terms of sulfur content.
5. Limited Feedstock: Not suitable for high-asphaltene feeds (coking occurs).

i) Comparison of Visbreaking and Hydrocracking:

Aspect Visbreaking Hydrocracking

Mechanism Thermal cracking Catalytic with hydrogen

Hydrogen No Required
Aspect Visbreaking Hydrocracking

Pressure Low Very high

Conversion Low (10–20%) High (50–100%)

Product Quality Lower (olefins, sulfur present) Higher (saturated, clean)

Capital Cost Low Very high

Group 8: Comparison, Safety, and Economic Importance

This group synthesizes comparisons between processes and discusses safety measures and
economic significance.

a) Differences Between Hydrotreating and Hydrocracking:

Aspect Hydrotreating Hydrocracking

Remove impurities (S, N,

Objective Reduce molecular size (cracking)
metals)

No significant molecular size Significant conversion to lighter

Conversion
reduction products

Co-Mo, Ni-Mo
Catalyst Bifunctional (acid + metal)
(monofunctional)

Pressure Moderate (20–100 bar) High (70–200 bar)

Hydrogen
Moderate High
Consumption
Aspect Hydrotreating Hydrocracking

Product Change Quality improvement only Quality improvement + yield shift

b) Safety Measures in Hydroprocessing Units:

Safety Aspect Measures

High Pressure Pressure relief systems; hydrostatic testing; thick-walled vessels

High Temperature Insulation; thermal monitoring; emergency depressurization

Hydrogen
Continuous LEL monitoring; inert gas purging; leak detection
Flammability

Hydrogen Sulfide H₂S monitoring; personal protective equipment; scrubbers

Pyrophoric catalysts require inert atmosphere; special

Catalyst Handling
loading/unloading procedures

Emergency Systems Emergency shutdown; depressurization systems; flare systems

c) Environmental Benefits of Hydrocracking and Hydrotreating:

1. Cleaner Fuels: Produces ultra-low sulfur diesel (ULSD) meeting environmental

regulations.
2. Reduced SOₓ Emissions: Lower sulfur content in fuels reduces acid rain.
3. Lower Particulate Matter: Cleaner diesel reduces particulate emissions.
4. Improved Efficiency: Produces higher-quality products with better combustion
characteristics.

d) Economic Importance of Hydrocracking in Refinery Industry:

Hydrocracking is a key process for maximizing value from heavy feedstocks. It allows
refineries to:

• Convert low-value residues into high-value distillates (jet fuel, diesel, naphtha)
 • Produce high-quality feedstocks for petrochemical units
• Achieve full conversion in a single process
• Integrate with downstream processes for maximum profitability

e) Process Control Parameters in Hydrotreating and Hydrocracking:

Parameter Effect

Higher temperature increases conversion but accelerates catalyst

Temperature
deactivation

Pressure Higher pressure improves hydrogenation and extends catalyst life

Hydrogen Partial
Higher hydrogen pressure suppresses coke formation
Pressure

Space Velocity Lower space velocity increases conversion but reduces throughput

Feedstock Quality Heavier, higher-sulfur feeds require more severe conditions

f) Types of Feedstocks Used in Hydrocracking and Visbreaking:

Process Feedstock

Hydrocracking Vacuum gas oil (VGO), deasphalted oil (DAO), heavy coker gas oil

Visbreaking Atmospheric residue (AR), vacuum residue (VR), heavy fuel oil

g) Role of Catalysts in Hydrocracking:

Hydrocracking catalysts are bifunctional:

• Acid Function: Provided by zeolites (Y-zeolite, ZSM-5) or amorphous silica-alumina;

responsible for cracking and isomerization.
• Hydrogenation Function: Provided by noble metals (Pt, Pd) or base metals (Ni-W, Ni-
Mo); responsible for saturating olefins, removing impurities, and preventing coke
formation.
h) Importance of Hydrogen in Refinery Processes:
Hydrogen is a critical utility in modern refineries, used in:

• Hydrotreating (HDS, HDN, HDM)

• Hydrocracking
• Catalytic reforming (net producer)
• Isomerization
• Hydrodesulfurization of FCC feed

Refineries often have dedicated hydrogen plants (steam reforming of natural gas) or recover
hydrogen from reformer off-gas.

i) Process Control Parameters in Visbreaking:

Parameter Effect

Higher temperature increases conversion but increases coke

Temperature
formation

Residence Time Longer residence time increases conversion but reduces stability

Quenching Temperature Critical for stopping reactions at desired conversion

Feedstock Composition Asphaltene content affects coking tendency