Mono-Olefins

Chapter 1. Mono-olefins Necessarily Arising in Various Processes

I. Introduction

II. The Gaseous or Low-boiling Olefins

III. The Gaseous Mono-olefins

A. Refinery Gases

B. Cracked Gases

C. The Gaseous Olefins from the Fischer-Tropsch Synthesis

D. The Gaseous Olefins from Coal

E. Ethylene in the Pyrolysis Gases from the Manufacture of Acetylene

IV. The Higher Olefins

A. General

B. Higher Olefins Arising as Unavoidable by-products

Chapter 2. The Direct Preparation of the Olefins

I. Introduction

II. The Dehydrogenation of Gaseous Paraffinic Hydrocarbons

A. Catalytic Dehydrogenation

B. Thermal Dehydrogenation

III. The Direct Manufacture of Gaseous Olefins by the Pyrolysis of Lower and Higher Aliphatic Hydrocarbons

A. Introduction

B. The Pyrolysis of Gaseous Paraffinic Hydrocarbons (Gas Cracking)

IV. The Direct Manufacture of Gaseous Olefins by the Pyrolysis of Higher Hydrocarbons, Particularly Petroleum and its Fractions, without the Simultaneous Production of Aromatic Hydrocarbons

A. The Kellogg Steam Pyrolysis Process

B. The Process for the Manufacture of Olefins by the Pyrolysis of Petroleum Oils and Petroleum Residues by Continuous Coking (Hoechst Coker Process)

C. The B.A.S.F. Fluidized-bed Process for the Manufacture of Ethylene from Crude Oils or Oil Residues Autothermally

D. The Lurgi-Ruhrgas Sand-Cracker

V. The Direct Manufacture of the Gaseous Olefins by the Pyrolysis of Aliphatic Hydrocarbons, Particularly Petroleum and its Fractions, with the Simultaneous Production of Aromatic hydrocarbons

A. General

B. The Technical Processes for the Manufacture of Olefins and romatic Hydrocarbons by the Pyrolysis of Aliphatic Hydrocarbons

VI. The Manufacture of Ethylene by the Partial Hydrogénation of Acetylene

A. General

B. General Remarks on the Partial Reduction of Acetylene

C. The Manufacture of Acetylene

D. The Technical Performance of the Partial Hydrogénation of Acetylene to Ethylene

E. The Manufacture of Ethylene Together with Acetylene

VII. The Manufacture of the Lower Olefins by the Catalytic Dehydration of Alcohols

VIII. The Manufacture of the Higher Olefins for their Own Sake

A. The Manufacture of the Higher Olefins by the Di-, Tri-, and Tetramerization of Normally Gaseous Olefins

B. Other Propene Polymerization Processes for the Preparation of the te tramer

C. The Di- and Trimerization of Ethylene over Cobalt on Active Carbon

D. The Polymerization of Gaseous Olefins over Nickel Oxide-silica-alumina Catalysts

E. The Mixed Polymerization of Propene with Isobutene

F. The Polymerization of Mixtures of Isohexene and Isoheptene

G. The Mülheim Synthesis of Olefins by the Directed Polymerization of Ethylene and its Homologues

H. Olefins from the Cracking of Paraffin Wax

I. The Laboratory-scale Preparation of Pure Olefins with a Strictly defined Position of the Double Bond

Chapter 3. The Concentration or Isolation of Olefins from Olefin-Containing Gases

I. General

II. The Distillation Processes

A. The Removal of Acetylene from Acetylene-containing Mixtures of Gases by Partial Hydrogénation to Ethylene

B. The Low-temperature Hydrogénation of Acetylenes of the C3 or C4 Fraction in the Liquid Phase

C. The Removal of Acetylene from the C2 Fraction by Distillation

D. The Separation of a Pyrolysis Gas by the Low-Temperature Pressure Distillation Process (Compression-Condensation Process)

III. The Concentration of Aliphatic Gaseous Hydrocarbons and their Separation According to C-number by the Compression-absorption Process (Pressure Oil Wash)

A. The Working up of the Products of Propane Pyrolysis by the Compressionabsorption Process (Pressure Oil Wash) for Ethylene with Separation of the Total Absorbate from the Wash Oil and Subsequent Individual Separation According to C-number in the Absence of the Absorption Oil

B. The Combined Treatment of a Refinery and a Pyrolysis Gas by Means of the Compression-absorption Process with Separation of the Absorbate According to C-number in the Presence of the Absorption Oil

C. The Working up of the Gases from Catalytically Cracked Gas-oils by the Absorption Process

D. The Selective Absorption of Ethylene in Copper Salt Solutions

IV. The Removal of Hydrocarbons from Hydrocarbon-poor Gases and their Separation According to C-number Continuously by the Adsorption Process

A. The Hypersorption Process

B. The Separation of the C3 Fraction ( P-P Fraction)

C. The Separation of the B-B Fraction into its Constituents

D. Separation of the Isoamylenes from a C5 Fraction from Catalytic Cracked Gasolines

E. The Separation of Mixtures of Low-molecular-weight Olefins and Paraffins with Similar Boiling Points by Extractive Distillation

Chapter 4. The Manufacture of High-Efficiency Carburettor Fuels

I. Introduction

A. The Knocking Behavior of Carburettor Fuels (Octane Number)

B. General Remarks on the Processing of Petroleum Oils

II. The Thermal and Catalytic Cracking of Petroleum and its Fractions

A. The Composition of Petroleum Oils

B. Fundamental Considerations on the Cracking of Hydrocarbons under the Conditions of Gasoline Manufacture

C. The primary Reactions in the Thermal Cracking Process

D. The Secondary Reactions in the Thermal Cracking Process

E. The practice of Thermal Cracking

F. The Starting Materials for the Thermal Cracking Processes and the Conditions of their Treatment

G. Catalytic Cracking

H. The Catalytic Reforming Processes

Chapter 5. The Working Up of Lower, Normally Gaseous, Paraffins and Mono-Olefins to give Carburettor Fuels

I. Introduction

II. The Polymerization of Olefins to Give Carburettor Fuels

A. Thermal Polymerization

B. Catalytic Polymerization

III. The Alkylation of the Paraffins with Olefins

A. General

B. The Thermal Alkylation of the Paraffins

C. The Catalytic Alkylation of the Isoparaffins with Olefins

IV. Reaction Mechanism of the Thermal and Catalytic Polymerization, Cracking, Alkylation, and Isomerization Processes

A. General

B. Reactions Involving Free Radicals

C. Reactions Involving Carbonium Ions

D. The Course of the Catalytic Alkylation Reaction in the Light of the Carbonium Ion Theory

Chapter 6. The Chlorination of the Olefins

I. General (Additive and Substitutive Chlorination)

II. The Relationship between Substitutive and Additive Chlorination

III. Substitutive Chlorination

A. The Substitutive Chlorination of the Tertiary Olefins (Methallyl Chloride)

B. The Cubstitutive Chlorination of Straight-chain Olefins — The High Temperature Chlorination of Propene (Allyl Chloride)

C. The Chemical Utilization of the Products of the Substitutive Chlorination of the Olefins

IV. The Additive Chlorination of the Olefins

A. General

B. The Industrial Manufacture of Ethylene Chloride from Ethylene and Chlorine

C. The Additive Chlorination of the Olefins by the Simultaneous Addition of Chlorine and Water (Hypochlorous Acid) with the Formation of Chlorohydrins

D. The Additive Chlorination of Olefins by Hydrochlorination

Chapter 7. The Hydration of Olefins to Alcohols

I. Hydration by Means of Sulphuric Acid

A. Introduction

B. The General Position in the field of the Lower Aliphatic Alcohols

C. The History of the Hydration of Olefins to Alcohols by Means of Sulphuric Acid

D. The Manufacture of Ethanol by the Hydration of Ethylene by Means of Sulphuric Acid

E. Other Processes for the Manufacture of Ethanol from Ethylene

II. The Direct Hydration of the Olefins to Alcohols with Fixed-bed Catalysts

III. The Industrial Uses of Ethanol

IV. The Manufacture of Isopropanol by the Hydration of Propene Using Sulphuric Acid

A. The Manufacture of Isopropanol by the Strong Acid Process

B. The Weak Acid Process for Hydrating Propene to Isopropanol by Means of Sulphuric Acid

C. The Manufacture of Isopropanol and Butan-2-ol in a Stationary System

V. The Direct Hydration of Propene by Passing it with Steam Over Fixed Tungsten Catalysts

VI. The Dehydrogenation to Ketones of the Secondary Alcohols Obtainable by Hydrating Olefins

A. General

B. The Industrial Method for the Dehydrogenation of Secondary Alcohols to Ketones

VII. The Sulphation of the Higher Olefins

A. General

B. The Higher Secondary Alkyl Sulphates

Chapter 8. Various Addition Reactions of the Olefins

A. The Addition of Hydrogen Sulphide, Sulfur, and sulfur-containing Compounds to Olefins

(a) The Addition of Hydrogen Sulphide to Olefins with the Formation of Mercaptans

(b) The Reaction of Olefins with Sulfur

(c) The Reaction of Olefins with Sulfhur Dioxide

(d) The Action of Sulphuryl Chloride on Olefins

(e) The Addition of Disulfur Dichloride and Sulphenic Acid Chlorides to Olefins

(f) The Action of sulfur Trioxide on Olefins

(g) The Addition of Bisulphites to the Olefinic Double Bond

B. The Addition of Formaldehyde to Olefins (Peins Reaction)

C. The Nitro-olefins

D. The Addition of Fydrogen to Olefins

E. The Addition of Hydrogen Halides and Halogens to Olefins

(a) The Addition of Hydrogen Halides to Olefins

(b) The Addition of Hydrogen Bromide Contrary to Markovnikov's Rule (Peroxide Effect)

(c) The Addition of Halogens to the Olefinic Double Bond

F. The Addition of Nitrosyl Chloride to Olefins

G. The Reaction of the Olefins with Dinitrogen Tetroxide

H. The Addition of Phosphine to Olefins

I. The Addition of Chloroethers to Olefins

J. The Action of Dithiocyanogen on Olefins

K. The Condensation of Chloral with Olefins

L. The Addition of Alcohols to the Olefinic Double Bond

M. The Addition of Hydrocyanic Acid and Nitriles to Olefins

N. The Addition of Cyanogen Chloride to Olefins

O. The Reaction of Olefins with Chromyl Chloride

P. The Reaction of Olefins with Chlorides of Phosphorus

Q. The Addition of Iodine 3,5-dinitrobenzoate to Olefins

R. The Reaction of Olefins with Alkyl Chlorides and their Derivatives

(a) The Reaction of Olefins with Alkyl Chlorides and their Derivatives in the Absence of Catalysts

(b) The Peroxide-catalysed Reaction of the Olefins with Alkyl Chlorides and their Derivatives

(c) The Addition of Carbene and Cloro- and Dichlorocarbenes to Olefins

S. The Addition of Boron Hydrides to Olefins

T. The Addition of Silicon Halides

U. The Reaction of Olefins with Acetyl Chloride and Acetic Anhydride

V. The Reaction of Olefins with Maleic Anhydride

W. The Reaction of Olefins with Metal Compounds

(a) The Action of Alkali-metal Alkyls on Olefins

(b) The Reaction of Metal Salts with Olefins

X. The Addition of Ammonia to Olefins

Y. The Addition of Carboxylic Acids to Olefins

Z. The Oxidation of Olefins

(a) The Oxidation of Olefins without Rupture of the Carbon Skeleton

Chapter 9. The Hydroformylation of the Olefins (ROELEN reaction; Oxo reaction)

I. Introduction

II. General Remarks on the Oxo Reaction

A. The Starting Material

B. The Catalyst

C. The Carbon Monoxide-hydrogen Mixture

D. The Influence of Pressure and Temperature on Hydroformylation

E. Hydrogénation of the Reaction Products of the Oxo Reaction in a Heterogeneous System

F. The Reaction Mechanism of Hydroformylation

G. The Catalytic Hydrogénation of the Formyl Group with Cobalt Hydrocarbonyl in a Homogeneous System

H. The Side Reactions in Hydroformylation

I. The Constitution of the Alcohols

K. The Possibilities of Application of the Products

L. Other Possibilities for the Manufacture of Higher Alcohols

M. The Influence of the Constitution of Oxo Alcohols on the Properties of the Commercial Products Manufactured from them

III. The Practical Performance of the Oxo Reaction

A. The Hydroformylation of Normally Liquid Olefins

B. The Hydroformylation of the Gaseous Olefins

IV. Other Reactions of Olefins with Carbon Monoxide

A. The Reaction of Olefins with Carbon Monoxide and Steam to form Carboxylic Acids

B. The Reaction of Olefins with Carbon Monoxide in the Presence of Alcohols

C. The Reaction of Olefins with Carbon Monoxide and Water in the Presence of Nickel Carbonyl According to Reppe

D. The Production of Alcohols by the Action of Carbon Monoxide and Water on Olefins in the Presence of Iron Hydrocarbonyls

E. The Action of Carbon Monoxide and Amines on Olefins

F. The Homologation Reaction (Action of Water-gas on Alcohols in the Presence of Cobalt Catalysts)

G. The Action of Carbon Monoxide and Water on Olefins in the Presence of Acid Catalysts with the Formation of Branched Carboxylic Acids (Koch Reaction)

Chapter 10. The Polymerization of the Mono-olefins to give Plastics and Lubricants

I. General

II. The Polymerization of Isobutene to Polyisobutene (Vistanex, Oppanol B , and Butyl Rubber)

A. General

B. The Influence of Impurities on the Polymerization of Isobutene

C. The Heat Effect of the Reaction and its Control

D. The Industrial Manufacture of Polyisobutene (Oppanol B)

E. The Polymerization of Isobutene to Give Oils by Means of Boron Fluoride

F. Butyl Rubber

III. The Polymerization of Ethylene to Polyethylene

A. General

B. Historical

C. The Industrial Work on the Polymerization of Ethylene to Polyethylene

D. Telomerization

IV. The Polymerization of the Mono-olefins to Give Lubricating Oils

A. General

B. The Operation of the Polymerization Reaction

C. The Starting Materials for the Polymerization of Mono-olefins to Lubricating Oils

D. The Connection Between the Properties of the Synthetic Lubricating Oils and the Constitution of the Olefins Used as Starting Materials

E. Experiments with Normally Liquid Olefins

F. Experiments with Normally Gaseous Olefins

G. The Industrial Manufacture of Lubricating Oils by Polymerizing Lower Mono-olefins

V. The Polymerization of the Higher Olefins to Lubricating Oils

A. The Starting Materials

B. The Industrial Process for the Polymerization of Higher Olefins

C. The Polymerization of the Higher Olefins at Pölitz

D. Mixed Polymerization

E. The Manufacture of the Anhydrous Aluminum Chloride

F. The Ester Oils

Chapter 11. The Alkylation of Aromatic Compounds with Olefins

I. General

II. The Alkylation of Aromatics with Olefins in the Presence of Anhydrous Aluminum Chloride as Catalyst

A. The Manufacture of Ethylbenzene

B. The Alkylation of Aromatics with Olefins in the Presence of Anhydrous Aluminum Chloride as Catalyst for the Preparation of Synthetic Lubricants and Auxiliaries for the Lubricating Oil Industry

C. The Dehydroalkylation of Aromatics with Isoparaffins

D. The Alkylation of Phenols with Olefins in the Presence of Anhydrous Aluminum Chloride

E. The Alkylation of Aromatic Amines

F. The Alkylation of Thiophen

III. The Manufacture of Eumene by the Catalytic Alkylation of Benzene with Propene

A. The Manufacture of Eumene by the Vapor-phase Alkylation of Benzene with Propene in the Presence of Phosphoric Acid Catalysts

B. The Industrial Manufacture of Eumene by the Vapor-phase Alkylation of Benzene with Propene in the Presence of Phosphoric Acid Catalysts

C. The Manufacture of Eumene by the Liquid-phase Alkylation of Benzene with Propene in the Presence of Sulphuric Acid as Catalyst

D. The Industrial Manufacture of Eumene by the Liquid-phase Process

E. Phenol and Acetone from Eumene

F . The "Dry" Oxidation of Eumene to Eumene Hydroperoxide

IV. The Alkylation of Aromatics for the Manufacture of Intermediates for Synthetic Detergents

A. The Alkylation of Benzene with Propene Polymerizate in the Presence of Anhydrous Hydrofluoric Acid as Catalyst

B. The Manufacture of Styrene from Ethylbenzene

C. The Dehydrogenation of Ethylbenzene to Styrene

D. Remarks on the Polymerization of Styrene

Chapter 12. Double-bond Isomerization in the Mono-olefins and its Practical Importance

I. Introduction

II. Possibilities of the Spontaneous Double-bond Isomerization of Olefins

A. Bond-isomerization in the Hydrogénation of Olefins with Nickel Catalysts

III. Possibilities of Double-bond Isomerization in the Industrial Manufacture of Olefins

A. Double-bond Isomerization in the Catalytic Dehydrochlorination of Alkyl Chlorides

B. Double-bond Isomerization in the Catalytic Dehydration of Alcohols

C. Dehydration and Dehydrochlorination without Bond Isomerization

D. The Higher Olefins of Chemical Industry

E. The Higher Olefins from the Di-, Tri-, and Tetramerization of Lower Olefins

IV. Possibilities of Bond-isomerization during the Chemical Treatment of Olefins

A. Bond-isomerization in the Sulphation of Olefins

B. Bond-isomerization in the Oxo Reaction (Hydroformylation)

C. The Influence of the Position of the Double Bond on the Quality and Yield of the Lubricating Oils Obtainable from Olefins by Polymerization

V. Practical Induction of Bond-isomerization in Order to Improve the Octane Numbers of Olefinic Carburettor Fuels Obtained by the Thermal Cracking of Higher Petroleum Fractions

A. General

B. The Knocking Behavior of Various Gasolines and Individual Unsaturated Hydrocarbons

C. Industrial Measures to Improve the Knock Resistance of Olefinic Gasolines by Bond-isomerization — RCH Process

D. Bond-isomerization in the Catalytic Desulphuration of Gasolines from Thermal Cracking by "Selective Hydrotreating" with Tungsten Sulphidenickel Sulphide Catalysts

VI. The "Contrathermodynamic" Displacement of the Double Bond from the Center Towards the End of the Molecule. Conversion of Olefins with Internal Double Bonds into α-Olefins

Index