Che 261

Here are detailed lecture notes for Lecture 2: Structure of the Chemical Industry based on
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Lecture 2: Structure of the Chemical

Industry
Course: CHE261: Chemical Process Industries​
Instructor: Dr. Raghavendra Ragipani​
Institution: IIT Kanpur​
Academic Year: 2023–24

1. Overview of the Chemical Industry

●​ The chemical industry plays a crucial role in modern society, transforming raw materials
into useful products.
●​ It is structured into various stages of processing, from raw materials to final products.

Industry Hierarchy:
Stage Number of Examples
Compounds

Raw Materials ~10 Oil, Natural Gas, Coal, Biomass, Rock, Sulfur, Air,
Water

Fuels ~10 LPG, Petrol, Diesel, Kerosene/ATF, Hydrogen

Intermediates ~300 Ethene, Propene, Butene, BTX, Syn Gas, Ammonia,

Methanol, Sulfuric Acid, Chlorine

Base ~20 Acetic Acid, Urea, Formaldehyde, Ethene Oxide,

Chemicals Acrylonitrile, Acetaldehyde, Terephthalic Acid

Final Products ~30,000 Plastics, Electronics, Fibers, Solvents, Detergents,

Pharmaceuticals, Insecticides, Perfumes

Key Takeaway:
 ●​ The transformation process follows a pyramid structure where a few raw materials
give rise to thousands of final products through various stages of chemical
processing.

2. Raw Materials in the Chemical Industry

Raw materials are the foundation of the chemical industry and include:

(a) Natural Gas

●​ Composed mostly of methane (CH₄) along with lighter alkanes.

●​ Can contain non-hydrocarbon impurities such as CO₂, H₂S, and N₂.
●​ Categorized as:
○​ Dry Gas: Mostly methane.
○​ Wet Gas: Contains heavier hydrocarbons.
○​ Sour Gas: Contains significant amounts of H₂S (needs processing).
○​ Sweet Gas: Free from or has minimal H₂S.

(b) Crude Oil

●​ A complex mixture of alkanes, cycloalkanes, and aromatics.

●​ Classified based on:
○​ Lighter vs. Heavier Crude: Based on hydrocarbon chain length.
○​ Sour vs. Sweet Crude: Based on sulfur content.

(c) Coal

●​ Rich in polycyclic aromatic hydrocarbons (PAHs).

●​ Contains mineral matter that can lead to ash formation.

(d) Biomass

●​ Derived from plant-based materials such as:

○​ Oils & Fats.
○​ Sugars.
○​ Lignocellulose: Made up of cellulose, hemicellulose, and lignin.
●​ Biomass contains high oxygen content and some ash.

3. Products Derived from Coal

Coal-based chemical production has historical importance, particularly in Germany (Prandtl,
1933).​
Coal-derived products include:

●​ Synthetic fuels.
●​ Methanol and ammonia production.
●​ BTX (Benzene, Toluene, Xylene).
●​ Coke (used in steel manufacturing).

4. Survey of the Petrochemical Industry

Petrochemicals form the backbone of modern chemical industries.​
Key components:

●​ Lower Alkenes: Ethylene, Propylene, Butenes.

●​ Aromatics: BTX (Benzene, Toluene, Xylene).
●​ Synthesis Gas: Mixture of CO and H₂ used for methanol, ammonia, and
Fischer-Tropsch processes.
●​ Oxygen, Nitrogen, and Sulfur-containing compounds.

5. Volume and Value Trends in the Chemical Industry

The chemical industry is structured based on:

1.​ Production Volume:​

○​ Base Chemicals: Produced in large volumes (e.g., ethylene, methanol).

○​ Intermediate Chemicals: Used to manufacture more complex products.
○​ Advanced Chemicals: Produced in lower volumes but have high value (e.g.,
pharmaceuticals, agrochemicals).
2.​ Complexity & Value:​

○​ As complexity increases, the value of the chemical product rises.

○​ High-value products include plastics, synthetic fibers, elastomers,
pharmaceuticals, consumer chemicals, etc.

6. World Oil Demand

 ●​ Global oil consumption is dominated by transportation (79%).
●​ Other uses:
○​ Petrochemicals: 6.5%.
○​ Asphalt: 2.5%.
○​ Heat generation: 11%.
○​ Lubricants: 1%.

Key Insight:

●​ The chemical industry only consumes a small fraction (6.5%) of crude oil, but this
fraction is essential for producing plastics, chemicals, and synthetic materials.

7. Energy from Fossil Fuels

Major Sources of Energy in the Chemical Industry:

1.​ Process Heating:

○​ Uses Natural Gas (NG) and Fuel Oil.
2.​ Steam Generation:
○​ Steam is categorized into different grades based on pressure and temperature:
Steam Type Pressure Temperature (K)
(bar)

High Pressure (HP) 40 523

Medium Pressure (MP) 10 453

Low Pressure (LP) 3 407

○​ Steam is used for heating, power generation, and chemical reactions.

3.​ Electricity Generation:
○​ Uses Natural Gas and Coal.
○​ Coal-based electricity is sometimes produced using Integrated Gasification
Combined Cycle (IGCC) for better efficiency.

8. Fossil Fuel Demand Projection (1990-2050)

●​ Fossil fuel demand is expected to decline gradually as renewable energy sources
emerge.
 ●​ The chemical industry must adapt by exploring alternative feedstocks and cleaner
technologies.

9. Chemical Market in India

●​ The global chemical market is valued at over $3.5 trillion.
●​ India’s chemical industry is growing and plays a significant role in:
○​ Fertilizers.
○​ Pharmaceuticals.
○​ Petrochemicals.
○​ Consumer goods.

10. Sulfur in the Chemical Industry

●​ Sulfuric acid (H₂SO₄) is one of the most important base chemicals.
●​ Uses:
○​ 65% of sulfuric acid is used in fertilizer production.
○​ Also used in ore processing and chemical synthesis.
●​ Shift in sulfur sourcing:
○​ Earlier, sulfur was mined from natural deposits.
○​ Now, it is recovered as a by-product from petroleum refining and natural gas
processing.

11. Future of the Chemical Industry

●​ Key questions for sustainability:​

○​ Can biomass replace fossil fuels?

○​ Can CO₂ be converted into useful chemicals?
●​ Research is ongoing to develop:​

○​ Bio-based alternatives to petrochemicals.

○​ CO₂ capture and utilization (CCU) technologies.
12. Reading Material
●​ Chapters 1 & 2 from:
○​ Jacob A. Moulijn & Michiel Makkee, “Chemical Process Technology” (2nd
Edition).

Summary of Key Concepts

Topic Key Takeaways

Chemical Industry Structure Few raw materials → Many products

Raw Materials Oil, gas, coal, biomass

Energy Use Process heat, steam, electricity

Fossil Fuel Demand Expected to decline in the future

India’s Chemical Market Growing and globally significant

Sulfur Mainly used in fertilizer production

Future Trends Biomass-based chemicals, CO₂ utilization

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These detailed notes will help in understanding the structure and dynamics of the chemical
industry. Let me know if you need further clarifications!

Lecture Notes on Petroleum Refining

Lecture 6-8: Petroleum Refining
Course: CHE261: Chemical Process Industries​
Instructor: Dr. Raghavendra Ragipani​
Institution: IIT Kanpur

1. Refinery Operations
 ●​ Crude oil is processed into refined products and specialty products.
●​ Refinery Products:
○​ Petroleum gases: Methane, Ethane, Propane, Butane, LPG (C3, C4)
○​ Light Distillates: Light Naphtha, Heavy Naphtha, Gasoline
○​ Middle Distillates: ATF/Kerosene, Diesel, Gas oils, Fuel oils
○​ Residual Fuel Oils: Heavy distillates
○​ Specialty Products: Lubricants, Engine oil, Greases, Waxes, Bitumen,
Petroleum coke, Carbon black

2. API Gravity

●​ A measure of crude oil heaviness:

○​ High API Gravity → Low Specific Gravity (SG) → Lighter crude
○​ Low API Gravity → High SG → Heavier crude
●​ Formula:

3. Carbon Number & Boiling Points

●​ Correlation between carbon range and boiling points:
Product Carbon Range Lower B.P. (°C) Upper B.P. (°C)

Refinery Gas 1-4 -161 -1

LPG 3-4 -42 -1

Naphtha 5-17 36 200

Gasoline 4-12 -1 216

Kerosene/Diesel 8-18 126 258

ATF 8-16 128 287

Fuel Oil 12-20+ 216 >421

Lubricating oil/Asphalt >20 >343 -

Coke ~50 >1000 -

4. True Boiling Point (TBP) Curve

●​ Represents the temperature at which different fractions of crude oil distill at standard
atmospheric pressure.
●​ Helps determine cut points for refinery fractions.
●​ If TBP is available at 40 mmHg, it needs interpretation for atmospheric crude distillation
units (CDU).
5. Properties of Petroleum Products

●​ Autoignition temperature: The minimum temperature required to ignite fuel without an

external ignition source.
●​ Flash Point: The lowest temperature at which vapors of a fuel can ignite in air.
●​ Octane Number & Cetane Number:
○​ Octane Number: Measures gasoline resistance to knocking.
○​ Cetane Number: Measures diesel fuel ignition delay.
●​ Reid Vapor Pressure (RVP): Indicates fuel volatility.

6. Fuel Characteristics
Distillate Flash Point (°C) Ignition Temperature (°C)

Petrol/Gasoline -23 >247

Diesel 55 210

Toluene 4 535

Ethyl Acetate -4 470

7. Fuel Standards (BSVI Specifications)

●​ BSVI Gasoline:
○​ Sulfur Content: <10 ppm
○​ Octane Number (RON): >91/95
○​ Aromatics: <35 vol%
○​ Benzene: <1.0 vol%
○​ Olefin: <21/18%
○​ Lead: <5 mg/L
○​ Oxygen content: <2.7 wt%
●​ BSVI Diesel:
○​ Sulfur Content: <10 ppm
○​ Cetane Number: >51
○​ T95: <370°C
○​ Polycyclic Aromatics: <11 wt%
○​ Flash Point: >35°C

8. Refinery Processes

Crude Desalting

●​ Purpose: Prevent fouling and corrosion by removing salts.

●​ Process: Oil-water separation using chemical interactions where salts dissolve in water.
 ●​ Principles: Density-based separation and electrostatic coalescence.
●​ Challenges:
○​ Emulsion formation
○​ Density variation in crude oil (low API crudes have similar densities to water)
●​ Process Flow:
○​ Crude oil is mixed with fresh water
○​ Heated to ~150°C
○​ Electric field used to separate water droplets
●​ Key Questions & Answers:
○​ How does crude oil density & viscosity affect separation?
■​ Higher density and viscosity make separation difficult as heavier crude
reduces the settling rate of water droplets.
○​ Why is more fresh water added?
■​ Additional fresh water enhances dilution and assists in washing out more
salts.
○​ How does surface tension affect emulsification?
■​ Lower surface tension promotes emulsion formation, making separation
challenging.
○​ Why do heavy naphthenic crudes form emulsions?
■​ They contain polar compounds that stabilize emulsions, making
separation harder.
○​ Does crude partially vaporize at 150°C?
■​ Yes, light components may vaporize, requiring careful temperature
control.
○​ When is two-stage desalting required?
■​ When crude has very high salt content or excessive emulsification occurs.

Crude Oil Distillation

●​ Objective: Separation of valuable products via distillation.

●​ Principles:
○​ Separation based on relative vapor pressure differences.
○​ Steam stripping for better fractionation.
●​ Challenges:
○​ Energy consumption
○​ Thermal cracking at high temperatures
○​ High percentage of bottoms fraction
●​ Process Flow:
○​ Desalted crude heated to 340-400°C.
○​ Sent to Atmospheric Distillation Unit (ADU).
○​ Separates into various distillate fractions:
■​ Gases → LPG Recovery
■​ Light Distillates → Naphtha
■​ Middle Distillates → Kerosene, Diesel
■​ Residue → Sent to Vacuum Distillation Unit (VDU)
Summary

●​ Petroleum refining involves a sequence of processes including desalting, distillation,

and further processing to obtain different fuel and specialty products.
●​ API gravity helps classify crude oil as light or heavy.
●​ Different fuel fractions have specific boiling point ranges and properties.
●​ BSVI specifications ensure fuel quality in terms of sulfur content, octane/cetane number,
and emissions compliance.
●​ Crude desalting and distillation are crucial steps in refining, with desalting focusing on
impurity removal and distillation on product separation.

Lecture 13: Petroleum Refining

Course: CHE261: Chemical Process Industries​
Instructor: Dr. Raghavendra Ragipani​
Institution: IIT Kanpur

1. Thermal Cracking

●​ Definition: An endothermic process that breaks large hydrocarbon molecules into

smaller, more valuable products at high temperatures.
●​ Key Features:
○​ Favored at higher temperatures.
○​ Leads to coking, where carbon deposits form on the reactor walls.
○​ Coking Impact:
■​ Reduces heat transfer efficiency.
■​ Can be useful in upgrading heavy refinery residues.

2. Crude Distillation Unit (CDU)

●​ Function: Separates crude oil into different fractions based on boiling points.
●​ Process:
○​ Crude oil is preheated to 340-400°C before entering the distillation column.
○​ Lighter fractions move to the top, heavier fractions settle at the bottom.
●​ Products: Refinery gases, light naphtha, heavy naphtha, kerosene/ATF, diesel,
atmospheric gas oil, atmospheric residue.

3. Vacuum Distillation Unit (VDU)

●​ Function: Processes atmospheric residue from CDU under reduced pressure.

●​ Purpose:
 ○​ Allows separation of heavy hydrocarbons at lower temperatures to prevent
cracking.
○​ Produces valuable streams like light vacuum gas oil (LVGO), heavy vacuum
gas oil (HVGO), and asphalt.
●​ Process Conditions:
○​ Vacuum preheater raises temperature to 380-450°C.
○​ Uses steam to reduce partial pressure and enhance separation.

4. Light Naphtha Stabilizer

●​ Feed: Low sulfur reformer (LSR) naphtha, primarily C5 and C6 hydrocarbons.

●​ Purpose:
○​ Removes excess butane and propane to limit Reid vapor pressure (RVP) in
gasoline.
○​ Ensures gasoline meets volatility specifications.
●​ Key Product Streams:
○​ Stabilized naphtha (used in gasoline blending).
○​ Propane and butane-rich stream (sent for LPG production).

5. Block Diagram of Separation Steps

●​ Flow Overview:
1.​ Crude from tank farm is pumped from ships/jetty.
2.​ Desalter removes salts at 120°C.
3.​ Preheater raises temperature to 340-400°C before distillation in CDU.
4.​ CDU Separation Products:
■​ Refinery gases, light naphtha, heavy naphtha, kerosene, diesel,
atmospheric gas oil, atmospheric residue.
5.​ VDU Process:
■​ Residue is further heated to 380-450°C for vacuum distillation.
■​ Produces LVGO, HVGO, and asphalt.
6.​ Byproducts:
■​ Oily water treatment.
■​ Refinery gases (C3, C4 fractions for LPG recovery).

6. Upgrading Low-Value Streams

●​ Objective: Enhance the quality and usability of lesser-value refinery fractions.

●​ Methods:
○​ Cracking: Converts heavy hydrocarbons into lighter fuels like gasoline and
diesel.
○​ Reforming: Improves octane number by converting low-octane naphtha into
high-octane reformate.
 ○​ Chemical Processing: Creates ethylene and propylene, which serve as
feedstocks for polymer production.

Summary

●​ Thermal cracking is essential for converting heavy fractions into lighter, valuable
products but can cause coking.
●​ CDU and VDU work together to refine crude oil and maximize product yield.
●​ Light naphtha stabilization ensures gasoline volatility control.
●​ Upgrading low-value streams is crucial for improving fuel quality and producing 1.
Introduction to Conversion Units
●​ Objective: Transform heavier hydrocarbons into valuable lighter products.
●​ Key Processes:
○​ Catalytic Cracking
○​ Coking
●​ Products of Cracking:
○​ High-octane gasoline from gas oils.
○​ Light olefins (ethylene, propylene) used for polymer production.

2. Fluidized Catalytic Cracking (FCC)

●​ Catalyst Role:
○​ Lowers activation energy and enhances reaction rate.
○​ Selective compound access through solid pore structures (e.g., silica-alumina,
zeolites).
●​ Why Fluidized Catalytic Cracking?
○​ Coking deactivates catalysts.
○​ Rapid regeneration of the catalyst is essential.
○​ Reactor-regenerator design ensures continuous operation.

3. FCC Process Overview

●​ Key Components:
○​ Reactor: Cracking reactions occur.
○​ Regenerator: Removes coke deposits and restores catalyst activity.
○​ Cyclone Separator: Separates solid catalyst particles from gas phase products.
○​ Distillation: Separates final hydrocarbon products.
●​ Product Streams:
○​ Gas
○​ Gasoline
○​ Cycle oil
○​ Slurry oil
●​ Additional Components:
○​ Pre-heater for feed preparation.
 ○​ Air supply for catalyst regeneration.
○​ Flue gas removal system.

4. Key Considerations in FCC Operations

●​ Is FCC an Isothermal Reactor?

○​ No, it operates with significant temperature variations due to exothermic
regeneration and endothermic cracking.
●​ Energy Balance in FCC:
○​ Requires careful temperature control in the reactor outlet.
○​ Heat generated during coke burning in the regenerator compensates for the
cracking heat demand.
●​ Impact of Spent Catalyst with More Coke:
○​ Increased coke on the catalyst affects the heat balance.
○​ Higher coke levels require additional air in the regenerator.
○​ Excessive coke buildup may lead to inefficient regeneration and loss of catalyst
activity.

Summary

●​ FCC is a crucial process for producing high-value fuels and petrochemicals.

●​ Catalysts enable selective cracking, and fluidized operation allows efficient
regeneration.
●​ Energy balance is a key factor in FCC operation, with coke buildup affecting process
efficiency.
●​ FCC reactor-regenerator design ensures continuous fuel production with minimal
downtime.
●​ chemical feedstocks.

Lecture 15: Petroleum Refining

Course: CHE261: Chemical Process Industries​
Instructor: Dr. Raghavendra Ragipani​
Institution: IIT Kanpur​
Academic Year: 2023–24
1. Delayed Coking
Overview:

●​ Type: Thermal cracking process (no catalyst required).

●​ Nature: Semi-continuous process.

Process Flow:

1.​ Feed: Vacuum residue.

2.​ Processing Units:
○​ Coking Drum Furnace: Heats the feed.
○​ Coking Drum: Cracks the heavy hydrocarbons.
○​ Fractionator: Separates the products.
3.​ Products:
○​ Petroleum Coke (solid carbonaceous residue).
○​ Lighter Products (such as gas, unstabilized naphtha, and gas oil).

2. Hydrotreating
Purpose:

●​ Hydrogen-based catalytic refining process used to:

○​ Saturate unsaturated bonds.
○​ Remove heteroatoms (S, N, O).
○​ Improve fuel quality.
○​ Reduce emissions.

Process Characteristics:

●​ Catalytic process with hydrogen addition.

●​ Exothermic reaction (heat is released).

Examples of Hydrotreating:

●​ Olefins saturation.
●​ De-aromatization.
●​ Desulfurization (HDS).
●​ Denitrogenation (HDN).

Process Flow:
 1.​ Feed: Hydrocarbon stream containing heteroatoms.
2.​ Hydrotreating Reactor: Uses a catalyst and hydrogen gas to remove impurities.
3.​ H2 Separator: Separates hydrogen from reaction products.
4.​ Products: Hydrotreated fuels with fewer impurities.

3. Heteroatom Removal (HDS & HDN)

Key Compounds in Crude Oil:

●​ Sulfur Compounds:
○​ Mercaptans (RSH).
○​ Sulfides (R₂S).
○​ Thiophenes (heterocyclic compounds).
●​ Nitrogen Compounds:
○​ Pyrrole (5-membered heterocyclic compound).
○​ Pyridine (benzene-like heterocyclic compound).
●​ Oxygen Compounds:
○​ Phenols.
○​ Peroxides.

Key Reactions:

1.​ Desulfurization (HDS):

○​ Example: RSH+H2→RH+H2SRSH + H_2 → RH + H_2S
2.​ Denitrogenation (HDN):
○​ Example: C4H4NH+4H2→C4H10+NH3C_4H_4NH + 4H_2 → C_4H_{10} +
NH_3
3.​ Deoxygenation:
○​ Example: C6H5OH+H2→C6H6+H2OC_6H_5OH + H_2 → C_6H_6 + H_2O
4.​ Cracking Reaction:
○​ Example: C10H22+H2→C4H10+C6H14C_{10}H_{22} + H_2 → C_4H_{10} +
C_6H_{14}

Trends in Sulfur Removal:

●​ Ease of removal: Paraffins > Naphthenes > Aromatics.

●​ Lower-boiling compounds are easier to desulfurize than higher-boiling ones.
●​ Nitrogen removal requires more severe conditions compared to sulfur removal.
4. Points to Consider in Hydrotreating
●​ Selectivity: Different catalysts are used:
○​ Co-Mo catalyst: Preferred for sulfur removal.
○​ Ni-Mo catalyst: Preferred for nitrogen removal.
●​ Hydrogen consumption: Amount depends on feed composition and reaction
conditions.
●​ Exothermic nature: Excess heat can impact reaction equilibrium and product quality.
●​ Reactor Type:
○​ Trickle bed reactors are commonly used.
●​ Key Reactions:
○​ Ring-opening reactions occur in denitrogenation.
○​ Hydrocracking can occur under severe conditions.
●​ By-products:
○​ Elemental sulfur is recovered from H₂S using the Claus Process.

5. Catalytic Reforming
Purpose:

●​ Converts hydrocarbons into aromatics.

●​ Increases the octane number of gasoline.

Process Characteristics:

●​ Catalytic process that rearranges hydrocarbon molecules.

●​ About 30% aromatics allowed in the final gasoline product (except in some special
cases).
●​ Boiling point changes are minimal.

Why is Catalytic Reforming Important?

●​ Aromatics enhance fuel quality.

●​ Reforming boosts the octane rating of gasoline.

Why LSR (Light Straight-Run) Naphtha Cannot Be Reformed?

●​ LSR naphtha contains too many paraffins and not enough aromatics.
●​ It does not produce sufficient high-octane reformate.
6. Catalytic Reforming Reactions
1.​ Paraffin → Naphthenes (Isomerization).
2.​ Naphthenes → Aromatics (Dehydrogenation).
3.​ Olefins → Paraffins → Above reactions follow.
4.​ Aromatics remain unchanged.

Process Flow:

●​ Feed: Naphtha.
●​ Catalyst: Typically Platinum-based.
●​ Products: High-octane gasoline with aromatics.

7. BTX (Benzene, Toluene, Xylenes) & Tatoray Technology

BTX Components:

●​ Benzene (C₆H₆): Used in petrochemicals.

●​ Toluene (C₇H₈): Used in solvents and octane boosters.
●​ Xylenes (C₈H₁₀): Key feedstock for polyester production.

Tatoray Technology:

●​ Converts C7 & C9 aromatics → C8 aromatics (Xylenes).

●​ Used to increase p-xylene yield (high-value product for polyester production).

Xylene Isomerization:

●​ Xylenes have similar physical properties, making separation difficult.

●​ Equilibrium-limited reaction process.

Summary of Key Concepts

Process Purpose Key Products

Delayed Coking Thermal cracking of heavy oil Coke, Naphtha, Gas oil

Hydrotreating Removes S, N, O impurities Low-sulfur fuels

 Catalytic Reforming Increases gasoline octane High-octane gasoline

BTX & Tatoray Produces aromatics for Benzene, Toluene,

industry Xylenes

🚀
These notes provide a structured and detailed overview of Lecture 15: Petroleum Refining for
study purposes. Let me know if you need further refinements or explanations!