Paraffins

Preface to the English Edition

Preface to the First German Edition

Introduction

Chapter 1. The Production and Manufacture of the Paraffinic Hydrocarbons

I. Introduction

II. The Production of the Lower Paraffins

A. The Production of the Lower Paraffinic Hydrocarbons from Natural Gases

B. The Gaseous Paraffins from the Hydrogenation of Lignite (Brown Coal)

III. Paraffin Wax

A. Petroleum Paraffin Wax

B. Paraffin Wax from Lignite Low-temperature Carbonization Tar and L.T.H. [Low Temperature Hydrogenation] Paraffin Wax

C. The Composition and Properties of the Various Paraffin Waxes

IV. Recovery of Normal Paraffinic Hydrocarbons by Extractive Crystallization from Petroleum Fractions by Means of Urea

V. Separation of Normal Paraffins from Technical Mixtures of Hydrocarbons by Means of Molecular Sieves

VI. Preparation of Pure Individual Paraffins

A. Straight-chain Paraffins

B. Branched Paraffins

References

Chapter 2. The Catalytic Hydrogenation of Carbon Monoxide over Cobalt and Iron Catalysts (Fischer-Tropsch Synthesis)

I. Introduction

II. The Hydrocarbon Synthesis of Franz Fischer and Hans Tropsch using Cobalt Catalysts

A. General

B. The Operation of the "Kogasin Synthesis" on a Technical Scale

C. The Normal-pressure Synthesis Process

D. The Medium-pressure Synthesis

E. The Olefin Synthesis

III. Hydrocarbon Synthesis Using Iron Catalysts

A. General

B. The Michael Process

C. The Duftschmid Process

D. The Kölbel-Rheinpreussen Process

E. The Fluidized-bed Process

F. The Isosynthesis

G. The Fischer-Tropsch Synthesis with Fixed Iron Catalyst (The Process of the Ruhrchemie-Lurgi Consortium)

H. The High- and Very-High-Molecular-Weight Paraffinic Hydrocarbons from the Fischer-Tropsch Synthesis

References

Chapter 3. The Chlorination and Chlorination Products of the Paraffins

I . Introduction

II. Photochemical Chlorination

A. Theoretical Considerations on Photochemical Reactions

B. The Practice of Photochemical Chlorination

III. Catalytic Chlorination

A. Homogeneous Catalysis

B. Heterogeneous Catalysis

IV. Thermal Chlorination

A. General. The Course of the Reaction in the Thermal Chlorination of Ethane

B. Laboratory Experiments on Thermal Chlorination

C. The Hass-Mcbee Thermal Chlorination Process

D. The Thermal Chlorination of Methane by the Hass-Mcbee Process

E. The Thermal Chlorination of the Gaseous Paraffins in the Presence of Suspended Materials. Basic Features of the Process

F. The Thermal Chlorination of Propane

G. The Thermal Chlorination of Pentane

H. The Thermal Chlorination of the Higher Paraffinic Hydrocarbons

V. Special Chlorination Processes

A. Chlorination with Chlorine Donors

VI. Perchlorination, High-pressure Chlorination, and Chlorolysis

A. The Working-up of the Reaction Products

VII. Preparation of Alkyl Chlorides Other than by the Direct Chlorination of Paraffinic Hydrocarbons

A. Replacement of the Hydroxyl Group in Alcohols by Chlorine

B. The Addition of Hydrogen Chloride or Alkyl Chlorides to Olefins

VIII. Reactions for Building up Highly Chlorinated Paraffinic Hydrocarbons

IX. The Prevention of the Formation of Di- and Ppoly Chlorides

X. The Formation of Isomers in the Mono-chlorination of Paraffinic Hydrocarbons

XI. The Bromoparaffins

XII. The Iodoparaffins

XIII. The Fluoroparaffins

XIV. The Chemical Utilization of the Chlorination Products of the Paraffinic Hydrocarbons

A. General

B. The Utilization of the Chlorination Products of the Lower Hydrocarbons

XV. The Utilization of the Chlorination Products of the Higher Paraffinic Hydrocarbons

A. General

B. Preparation of Synthetic Lubricating Oils from Chloroparaffins

C. The Condensation of Alkyl Chlorides with Nafthalene to Give Pour-point Depressants (Paraflow)

D. The Further Processing of Higher Alkyl Chlorides to Give Detergents and Textile Auxiliaries

References

Chapter 4. The Nitration and Nitration Products of the Paraffins

I. Introduction

II. The Reactions of the Nitroparaffins

A. Action of Alkali on the Nitroparaffins

B. The Reaction of the Nitroparaffins with Nitrous Acid

C. The Halogenation of the Nitroparaffins

D. The Sulfochlorination of the Nitroparaffins

E. Condensation of the Nitroparaffins with Compounds Containing Carbonyl Groups (Aldehydes and Ketones)

F. The Oxidation of the Nitroparaffins

G. The Reduction of the Nitroparaffins

H. The Action of Mineral Acids on the Nitroparaffins

I. Action of Diazonium Salts on the Aci-form of the Nitroparaffins

J. Addition of Nitroparaffins to Activated Double Bonds

III. The Direct Nitration of Normally Gaseous Paraffinic Hydrocarbons

A. General; Starting Material

B. Hass's Gas-fase Nitration Process

C. Special Data on the Nitration of the Lower Members of the Paraffinic Hydrocarbons

D. Gas-fase Nitration with Nitrogen Dioxide

E. The Gas-fase Nitration of Higher Paraffinic Hydrocarbons with Nitric Acid Vapor

F. Industrial Gas-fase Nitration

G. Nitration in the Presence of Oxygen and Halogens

H. Hass's Nitration Rules

IV. The Nitration of the Higher Paraffinic Hydrocarbons in the Liquid Phase

A. Nitration in a Heterogeneous System

B. Nitration in a Homogeneous System

C. The Starting Material for the Nitration of Higher Paraffinic Hydrocarbons

D. The Working up of the Nitration Products of the Higher Paraffinic Hydrocarbons

E. Properties and Composition of the Nitration Products of the Higher Paraffins

V. Preparation of the Mononitroparaffins by Methods Other than the Direct Nitration of Hydrocarbons

A. Victor Meyer's Reaction

B. The Synthesis Due to Kornblum Et Al.

C. Kolbe's Synthesis

D. Bewad's Synthesis

E. Further Preparative Possibilities

F. Preparation of Nitroparaffins with the Nitro Group in a Definite Position from Oximes

G. The Physical and Pharmacological Properties of the Lower-molecularweight Nitroparaffins

VI. The Utilization of the Nitration Products of the Lower Gaseous Paraffinic Hydrocarbons

A. General

B. The Use of the Lower Nitroparaffins as Solvents

C. The Reaction with Aldehydes in an Alkaline Medium to Give Nitroalcohols

D. Further Reactions of the Alifatic Nitroalcohols of Various Types

E. The Production of Carboxylic Acids by the Action of Mineral Acids on the Primary Nitroparaffins

F. Production of Aldehydes and Ketones by the Action of Mineral Acids on the Aci-form of the Nitroparaffins (NEF Reaction)

G. Various Reactions of the Lower Nitroparaffins

VII. The Further Processing of the Nitration Products of the Higher Paraffinic Hydrocarbons

A. General

B. Transformations of the Nitro Group

C. Reactions of the Hydrogen Atom in the a-Position to the Nitro Group

VIII. The Dinitroparaffins

A. Preparation by Direct Nitration

B. Preparation of the Dinitroparaffins Other than by the Direct Nitration of Paraffins

References

Chapter 5. The Sulfochlorination and the Sulfochlorination Products of the Saraffinis

I. Introduction

A. The History of the Sulfochlorination Reaction

B. The Actual Constitution of the Sulfochlorination Products

II. The Side-reactions in Sulfochlorination

A. Chain hlorination

B. The Formation of Di- and Polysulfonyl Chlorides

III. The Suppression of the Side-reactions in Sulfochlorination

A. The Substantial Avoidance of Chain Chlorination by the Use of Ultraviolet Light in the Sulfochlorination Reaction

B. The Influence of the Temperature on the Sulfochlorination Reaction

C. The Effect of the Ratio of Sulfur Dioxide to Chlorine in the Gas on the Chain Chlorination

D. The Probable Causes of the Residual Chain Chlorination

E. The Substantial Avoidance of the Formation of Di- and Polysulfonyl Chlorides

IV. The Reaction Mechanism of Sulfochlorination

V. Catalysts for Sulfochlorination

A. Radical-forming Substances

B. Organic Peroxides

C. Olefins as Catalysts for the Sulfochlorination Reaction

D. Inhibitors of the Sulfochlorination Reaction

VI. The Sulfochlorination of Paraffinic Hydrocarbons with Sulfuryl Chloride

VII. The Behavior of the Individual Types of Hydrocarbons in Sulfochlorination

A. The Normal Paraffins

B. The Cycloparaffins

C. Aromatic Compounds

D. Other Organic Compounds

E. Petroleum

F . Kogasin from the Fischer-Tropsch Synthesis

VIII. The Analytical Determination of the Products which Arise in Sulfochlorination

A. Determination of the Chain Chlorine

B. The Hydrolysable Chlorine

C. Determination of the Neutral Oil

D. Determination of the Amounts of Mono-, Di-, and Polysulfonyl Chlorides

E. The Chlorinated Mono- and Polysulfonyl Chlorides

IX. The Formation of Isomers in the Sulfochlorination of the Paraffinic Hydrocarbons

X. Preparation of the Alifatic Sulfonyl Chlorides by Methods Other than Sulfochlorination

A. The Thiourea Process of Sprague and Johnson

B. The Thiocyanate Process of Johnson and Douglass

C. The Reaction of Mercaptans, Sulfides, and Di- and Polysulfides with Chlorine Water

D. The Reaction of Paraffin Sulfonates with Phosforus Pentachloride

E. The Preparation of Definide Paraffin Sulfonyl Chlorides by Means of the Grignard Reaction

XI. Sulfonyl Bromides and Sulfonyl Fluorides

XII. The Reactions of the Alifatic Sulfonyl Chlorides

A. The Saponification of the Sulfonyl Chlorides with Alkali Hydroxides

B. The Reaction of the Sulfonyl Chlorides with Ammonia, Amines, and their Derivatives

C. The Reaction of the Alifatic Sulfonyl Chlorides with Phenols and their Derivatives

D. The Reaction of Paraffin Sulfonyl Chlorides with Alcohols and Thioalcohols

E. The Desulfurization of the Alifatic Sulfonyl Chlorides

F. The Reduction of the Sulfonyl Chlorides to Sulfinic Acids

XIII. The Technical Process of Sulfochlorination

A. The Sulfochlorination of Normally Gaseous Paraffinic Hydrocarbons

B. The Sulfochlorination of the Liquid Paraffinic Hydrocarbons

XIV. The Further Processing of the Sulfonyl Chlorides of the Higher Paraffins

A. General

B. The Separation of the Sulfonyl Chlorides from Neutral Oil by Extraction with Selective Solvents

C. The Further Processing of the Sulfonyl Chlorides of the Higher Paraffins in the Presence of Neutral OilD. Hypalon S2 562

E. Prospects for the Further Treatment of the Higher Paraffin Sulfonyl Chlorides

References

Chapter 6. The Oxidation and Oxidation Products of the Paraffins

I. Introduction

II. The Oxidation of the Normally Gaseous Paraffinic Hydrocarbons

III. The Incomplete Oxidation of Methane with Oxygen for the Preparation of Synthesis Gas (Carbon Monoxide-hydrogen Mixtures)

IV. The Catalytic Oxidation of Gaseous Paraffinic Hydrocarbons in a Homogeneous System

V. The Oxidation of Propane and Ethane for the Preparation of Hydrogen Peroxide

VI. Oxidation Processes for Producing Heat

VII. The Oxidation of the Higher Paraffinic Hydrocarbons

A. History of the Oxidation of Paraffin Wax

B. The Starting Material for the Oxidation of Paraffin Wax

C. True Paraffin Wax Oxidation

VIII. The Chemistry of the Oxidation Reaction

IX. The Utilization of the By-products of the Oxidation of Paraffin Wax

A. The Aqueous Condensate ("Condensate Liquor")

B. The Oily Condensate ("Condensate Oil")

C. The Fore-run Fatty Acids

D. Synthetic Fat

X. The Oxidation of Higher Paraffinic Hydrocarbons for Other Purposes than the Manufacture of Soap Fatty Acids

A. The Oxidation of Hard Paraffin Wax with Nitrous Gases in the Presence of Nitrosylsulfuric Acid

B. The Preparation of Alcohols by the Oxidation of Higher Paraffinic Hydrocarbons

C. The Oxidation of Higher Paraffinic Hydrocarbons in the Gas Phase

D. Dicarboxylic Acids by the Oxidation of Paraffinic Hydrocarbons

References

Chapter 7. The Sulfoxidation and Other Substitution Reactions of the Paraffinic Hydrocarbons

I. Introduction

II. The Starting Material

A. The Mechanism of the Sulfoxidation Reaction

III. Sulfoxidation in the Presence of Ultraviolet Light

A. Work on the Laboratory Scale

B. Discontinuous Process

C. Continuous Process

D. The Recovery of the Free Alkanesulfonic Acids

IV. Technical Sulfoxidation by the Light-water Process

A. Reaction Vessel

B. The Immersion Tubes

C. The Sources of Energy

D. The Introduction of the Gases into the Hydrocarbon Mixture

V. Sulfoxidation in the Presence of Peroxide Compounds

A. The Sulfoxidation of Paraffinic Hydrocarbons in the Presence of Organic Per-acids

B. The Sulfoxidation of Paraffinic Hydrocarbons in the Presence of Acyl Alkanesulfonyl Peroxides

VI. Sulfoxidation in the Presence of Substances with an Acylating Action

A. Laboratory Experiments

B. The Technical Process of Sulfoxidation in the Presence of Acetic Anhydride (The Acetic Anhydride Process)

VII. Sulfoxidation in the Presence of Ozone

VIII. The Formation of Isomers during Sulfoxidation

IX. Sulfoxidation in the Presence of Chlorine

X. Further Methods for the Preparation of Alkanesulfonates

XI. Other Substitution Reactions of the Paraffinic Hydrocarbons

A. Chlorofosfonation

B. Carbochlorination

C. Cyanation

D. The Nitrosochlorination and Nitrosation of the Paraffinic Hydrocarbons

E. The Reaction of Paraffinic Hydrocarbons with Carbon Monoxide in the Presence of Anhydrous Aluminum Chloride

F. Reaction of the Paraffinic Hydrocarbons with Acid Chlorides in the Presence of Anhydrous Aluminum Chloride

G. The Photochemical Formation of Sulfinic Acids from Sulfur Dioxide and Paraffinic Hydrocarbons

Xll. Various Chemical Reactions of the Paraffinic Hydrocarbons Other than Substitution Processes

A. The Action of Sulfur on Paraffinic Hydrocarbons

B. The Preparation of Thiofen from Paraffinic Hydrocarbons and Sulfur

C. The Preparation of Carbon Disulfide from Paraffinic Dydrocarbons and Sulfur

D. The Catalytic Reaction of Methane with Ammonia and Air at High Temperatures to Form Hydrocyanic Acid (Andrussoff Process)

E. Preparation of Nitriles from Gaseous Paraffinic Hydrocarbons and Ammonia in the Presence of Catalysts

F. The Preparation of Carbon Black from Gaseous Paraffinic Hydrocarbons

G. The Action of Various Radiations on Paraffinic Hydrocarbons

References

Chapter 8. The Isomerization of the Paraffinic Hydrocarbons

I. Introduction

II. General Remarks on the Isomerization of Paraffinic Hydrocarbons Using Anhydrous Aluminum Chloride as Catalyst

III. The Isomerization of n-Butane to Isobutane

A. The Catalyst

B. Hydrogen Chloride as Promoter of the Isomerization Reaction

C. The Influence of Olefins on the Isomerization Reaction

D. The Influence of Temperature on the Isomerization Reaction

V. The Isomerization of the Higher Paraffinic Hydrocarbons Using Anhydrous Aluminum Chloride as Catalyst

V. The Industrial Isomerization of Paraffinic Hydrocarbons Using Anhydrous Aluminum Chloride as Catalyst

A. The Isomerization of Butane

B . The Isomerization of Pentane and Hexane

C. The Catalytic Isomerization of Paraffinic Hydrocarbons without Using Aluminum Chloride

D. The Processes for the Catalytic Isomerization of Paraffinic Hydrocarbons without Aluminum Chloride

E. The Isomerization of Higher Paraffinic Hydrocarbons

F. The Separation of the Normal Paraffins from a Mixture with Isoparaffins by Means of Molecular Sieves

References

Chapter 9. The Substitution Behavior of Paraffinic Hydrocarbons

I. Introduction

A. The Importance of the Various Substitution Reactions of Paraffinic Hydrocarbons

B. The Oldest Substitution Reaction, Chlorination

C. Dumas' Substitution Theory

D. Why Were the Substitution Reactions of Paraffinic Hydrocarbons not Developed Until so Recently

E. Conceivable Possibilities for the Practical Application of Chlorination

F. Why can Chlorination not Assume the Prominent Position in Alifatic Chemical Technology which was Previously Considered Possible

G. The Causes of the Unsatisfactory Reaction Behavior of the Chlorination Products and their Connection with their Composition

II. The Composition of the Chlorination Products of the Paraffinic Hydrocarbons

A. The Older Investigations (Review)

B. The Work of Schorlemmer and his Co-workers

C. The Work of Michael and his Co-workers

D. Literature Data on the Quantitative Ratios in Substitution by Chlorination

III. New Accurate Investigations on the Substitution Behavior in Chlorination

A. The Formation of Isomers in the Monochlorination of Normally Gaseous Paraffins, including the Pentanes

B. The Rules Governing the Formation of Isomeric Halogenohydrocarbons by the Direct Chlorination of Gaseous Hydrocarbons

C. Example of the Calculation of the Yield of the Isomeric Monochlorides from the Relative Reaction Velocities of Primary, Secondary, and Tertiary Hydrogen Atoms

D. The Formation of Isomers in the Chlorination of Normally Liquid Paraffinic Hydrocarbons

IV. The Substitution Behavior in the Nitration of Paraffinic Hydrocarbons

A. Literature Data

B. Recent Investigations

C. Summary

V. Action of Nitrosyl Chloride on Heptane and Hexane

VI. Action of Sulfur Dioxide on Paraffinic Hydrocarbons in Ultraviolet Light

VII. Action of Cyanogen Chloride on Paraffinic Hydrocarbons in the Presence of Peroxides

VIII. Action of Phosforus Trichloride and Oxygen on Paraffinic Hydrocarbons

IX. Combined Action of Nitrogen Monoxide and Chlorine on Paraffinic Hydrocarbons in Ultraviolet Light

X. The Substitution Behavior in the Sulfochlorination of Paraffinic Hydrocarbons

A. The Composition of the Sulfochlorination Products of Normally Gaseous Paraffinic Hydrocarbons

B. The Composition of the Sulfochlorination Products of the Higher Paraffinic Hydrocarbons

C. Summary

XI. The Substitution Behavior in the Sulfoxidation of the Paraffinic Hydrocarbons

A. The Composition of the Sulfoxidation Products of the Higher Paraffinic Hydrocarbons

B. The Formation of Isomers from the Normally Gaseous Paraffinic Hydrocarbons

XII. The Substitution Behavior in the Chlorofosfonation of the Paraffinic Hydrocarbons

XIII. The Formation of the Individual Fatty Acids in the Oxidation of Paraffins

XIV. The Conditions for the Disubstitution of Paraffinic Hydrocarbons

A. The Disubstitution Behavior in the Chlorination of the Paraffinic Hydrocarbons

B. The Situation in the Disulfochlorination of Paraffinic Hydrocarbons

C. The Situation in the Sulfochlorination of Chlorinated Hydrocarbons and Sulfonyl Chlorides

D. The Situation in the Dinitration of Paraffinic Hydrocarbons

References

Index