Hydrocarbon chemistry

Автор(ы):Olah A.
06.10.2007
Год изд.:2003
Издание:2
Описание: Seven years passed since the publication of the first edition of our book. It is rewarding that the favorable reception of and interest in hydrocarbon chemistry called for a second edition. All chapters were updated (generally considering literature through 2001) by adding sections on recent developments to review new advances and results. Two new chapters were also added on acylation as well as emerging areas and trends (including green chemistry, combinatorial chemistry, fiuorous biphase catalysis, solvent-free chemistry, and synthesis via C02 recycling from the atmosphere). Because of its importance a more detailed treatment of chemical reduction of CO2 as a source for hydrocarbons is also included in Chapter 3. The new edition should keep our book current and of continuing use for interested readers. The authors hope that Hydrocarbon Chemistry will continue to serve its purpose and the goals that we originally intended.
Оглавление:
Hydrocarbon chemistry — обложка книги.
1. General Aspects
  1.1. Hydrocarbons and Their Classes [1]
  1.2. Energy-Hydrocarbon Relationship [2]
  1.3. Hydrocarbon Sources and Separation [4]
    1.3.1. Natural Gas [5]
    1.3.2. Petroleum or Crude Oil [6]
    1.3.3. Heavy Oils, Shale, and Tar Sand [7]
    1.3.4. Coal and Its Liquefaction [8]
  1.4. Petroleum Refining and Upgrading [10]
    1.4.1. Distillation of Crude Petroleum [10]
    1.4.2. Hydrocarbon Refining and Conversion Processes [11]
  1.5. Finite, Nonrenewable Hydrocarbon Resources [13]
  1.6. Hydrocarbon Synthesis [14]
    1.6.1. Syngas (CO—H(?))-Based Fischer-Tropsch Synthesis [15]
    1.6.2. Methyl Alcohol Conversion [16]
    1.6.3. Carbon Dioxide Conversion [17]
    1.6.4. Direct Methane Conversion [17]
  1.7. Chemical Nature of Hydrocarbon Conversion Reactions [20]
    1.7.1. Homolytic (Free-Radical) Reactions [20]
    1.7.2. Heterolytic (Ionic) Reactions [20]
  1.8. Use of Hydrocarbons [23]
    1.8.1. Refined Petroleum Products [23]
    1.8.2. Transportation Fuels [23]
    1.8.3. Chemicals and Plastics [25]
      References and Notes [25]
2. Hydrocarbon from Petroleum and Natural Gas [30]
  2.1. Cracking [30]
    2.1.1. Cracking Processes [30]
    2.1.2. Mechanism of Cracking [33]
    2.1.3. Comparison of Cracking Operations [36]
  2.2. Reforming [38]
    2.2.1. Thermal Reforming [39]
    2.2.2. Catalytic Reforming [40]
      Hydrofonning [40]
      Metal-Catalyzed Reforming [41]
  2.3. Dehydrogenation with Olefin Production [44]
    2.3.1. Thermal Dehydrogenation [45]
    2.3.2. Catalytic Dehydrogenation to Alkenes [46]
    2.3.3. Practical Applications [47]
      C(?)-C(?) Alkenes [47]
      C(?) Alkenes [48]
      1,3-Butadiene and Isoprene [48]
      Higher Olefins [49]
      Styrene [50]
  2.4. Upgrading of Natural-Gas Liquids [50]
  2.5. Aromatics Production [51]
    2.5.1. Catalytic Dehydrogenation and Dehydrocyclization [51]
    2.5.2. Practical Applications [56]
  2.6. Recent Developments [57]
    2.6.1. Cracking [57]
    2.6.2. Reforming [60]
    2.6.3. Dehydrogenation with Olefin Production [62]
      Catalytic Dehydrogenation [62]
      Oxidative Dehydrogenation [64]
    2.6.4. Aromatics Production [66]
      References [70]
3. Synthesis from C(?) Sources [85]
  3.1. Nature's C(?) Chemistry [86]
  3.2. The Chemical Reduction and Recycling of CO(?) [86]
    3.2.1. Catalytic Reduction [88]
      Heterogeneous Hydrogenation [88]
      Homogeneous Hydrogenation [94]
    3.2.2. Other Reductions [95]
      Ionic Reduction [95]
      Electrochemical and Electrocatalytic Reduction [96]
      Photoreduction [97]
      Enzymatic Reduction [99]
  3.3. Fischer-Tropsch Chemistry [100]
    3.3.1. Catalysts [102]
    3.3.2. Mechanism [103]
    3.3.3. Related Processes [107]
  3.4. Direct Coupling of Methane [109]
    3.4.1. Catalytic Oxidative Condensation [109]
    3.4.2. High-Temperature Self-Coupling [113]
  3.5. Hydrocarbons through Methane Derivatives [114]
    3.5.1. Hydrocarbons through Methanol [114]
      Methanol Synthesis [114]
      Methanol Conversion to Hydrocarbons [117]
    3.5.2. Hydrocarbons through Methyl Halides [123]
    3.5.3. Hydrocarbons through Sulfurated Methanes [123]
  3.6. Recent Developments [124]
    3.6.1. Fischer-Tropsch Chemistry [124]
      Fischer-Tropsch Synthesis [124]
      Related Processes [127]
    3.6.2. Direct Coupling of Methane [129]
      Catalytic Oxidative Condensation [129]
      Other Processes [130]
    3.6.3. Hydrocarbons through Methane Derivatives [132]
      Methanol Synthesis [132]
      Methanol Conversion to Hydrocarbons [136]
      References [137]
4. Isomerization [160]
  4.1. Acid-Catalyzed Isomerization [161]
    4.1.1. Alkanes [161]
      Mechanism [165]
    4.1.2. Arylalkanes [170]
      Side-Chain Isomerization [170]
      Positional Isomerization [170]
    4.1.3. Alkenes and Dienes [174]
  4.2. Base-Catalyzed Isomerization [177]
    4.2.1. Alkenes [177]
    4.2.2. The Reversible Acetylene-Allene Transformation [180]
  4.3. Metal-Catalyzed Isomerization [182]
    4.3.1. Alkanes [182]
    4.3.2. Alkenes [185]
  4.4. Pericyclic Rearrangements [189]
  4.5. Practical Applications [192]
    4.5.1. Isomerization of С(?)-С(?) Hydrocarbons [192]
      Alkanes [192]
      Alkenes [193]
    4.5.2. Isomerization of Xylenes [193]
  4.6. Recent Developments [194]
    4.6.1. Acid-Catalyzed and Bifunctional Isomerization [194]
      Alkanes [194]
      Alkenes [196]
      Xylenes [197]
      The Acetylene-Allene Rearrangement [198]
    4.6.2. Metal-Catalyzed Isomerization [199]
    4.6.3. Pericyclic Rearrangements [199]
      References [201]
5. Alkylation [215]
  5.1. Acid-Catalyzed Alkylation [215]
    5.1.1. Alkylation of Alkanes with Alkenes [215]
    5.1.2. Alkylation of Alkanes under Superacidic Conditions [221]
      Alkylolysis (Alkylative Cleavage) [225]
    5.1.3. Alkylation of Alkenes and Alkynes [225]
      Alkylation of Alkenes with Organic Halides [225]
      Alkylation of Alkynes [227]
      Alkylation with Carbonyl Compounds: The Prins Reaction [228]
    5.1.4. Alkylation of Aromatics [229]
      Catalysts [230]
      Alkylation with Alkyl Halides [232]
      Alkylation with Alkenes [238]
      Alkylation with Alkanes [241]
      Alkylation with Alcohols [244]
      Transalkylation and Dealkylation [246]
  5.2. Base-Catalyzed Alkylation [248]
  5.3. Alkylation through Organometallics [250]
  5.4. Miscellaneous Alkylations [253]
  5.5. Practical Applications [254]
    5.5.1. Isoalkane-Alkene Alkylation [254]
    5.5.2. Ethylbenzene [257]
    5.5.3. Cumene [258]
    5.5.4. Xylenes [258]
    5.5.5. (?)-Ethyltoluene [259]
    5.5.6. Detergent Alkylates [260]
  5.6. Recent Developments [260]
    5.6.1. Alkane-Alkene Alkylation [260]
    5.6.2. The Prins Reaction [262]
    5.6.3. Alkylation of Aromatics [262]
      Solid Acid Catalysts [262]
      Specific Examples [265]
      Side-Chain Alkylation [267]
      Transalkylation [268]
    5.6.4. Miscellaneous Alkylations [268]
      References [269]
6. Addition [284]
  6.1. Hydration [284]
    6.1.1. Alkenes and Dienes [285]
    6.1.2. Alkynes [287]
    6.1.3. Practical Applications [288]
      Production of Alcohols by Hydration of Alkenes [288]
      Production of Octane-Enhancing Oxygenates [289]
      Acetaldehyde [290]
  6.2. HX addition [290]
    6.2.1. Hydrohalogenation [290]
      Alkenes [290]
      Dienes [295]
      Alkynes [296]
    6.2.2. Hypohalous Acids and Hypohalites [297]
    6.2.3. Hydrogen Cyanide [299]
    6.2.4. Practical Applications [301]
      Ethyl Chloride [301]
      Hydrochlorination of 1,3-Butadiene [301]
      Vinyl Chloride [301]
      Ethylene Chlorohydrin [302]
      Propylene Chlorohydrin [302]
      Adiponitrile [303]
      Acrylonitrile [303]
  6.3. Halogen Addition [304]
    6.3.1. Alkenes [304]
    6.3.2. Dienes [308]
    6.3.3. Alkynes [310]
    6.3.4. Practical Applications [310]
      Vinyl Chloride [310]
      Chlorination of 1,3-Butadiene [312]
  6.4. Ammonia and Amine Addition [312]
    6.4.1. Alkenes [312]
    6.4.2. Dienes [313]
    6.4.3. Alkynes [314]
  6.5. Hydrometallation [315]
    6.5.1. Hydroboration [315]
      Alkenes [316]
      Dienes [319]
      Alkynes [320]
    6.5.2. Hydroalanation [321]
    6.5.3. Hydrosilylation [322]
      Alkenes [323]
      Dienes [324]
      Alkynes [325]
    6.5.4. Hydrozirconation [326]
  6.6. Halometallation [327]
  6.7. Solvometallation [329]
    6.7.1. Solvomercuration [329]
    6.7.2. Oxythallation [330]
  6.8. Carbometallation [330]
  6.9. Cycloaddition [332]
  6.10. Recent Developments [336]
    6.10.1. Hydration [336]
    6.10.2. Hydrohalogenation [336]
    6.10.3. Halogen Addition [337]
    6.10.4. Hydroamination [339]
    6.10.5. Hydrometallation [341]
      Hydroboration [341]
      Hydrosilylation [342]
      Hydrozirconation [344]
      Other Hydrometallations [345]
    6.10.6. Halometallation [345]
    6.10.7. Solvometallation [346]
    6.10.8. Carbometallation [346]
    6.10.9. Cycloaddition [347]
      References [349]
7. Carbonylation [371]
  7.1. Hydroformylation [371]
    7.1.1. Alkenes [372]
    7.1.2. Dienes and Alkynes [377]
    7.1.3. Synthesis of Aldehydes and Alcohols by the Oxo Reaction [377]
  7.2. Carboxylation [379]
    7.2.1. Koch Reaction [379]
    7.2.2. Carboxylation Catalyzed by Transition Metals [381]
      Alkenes and Dienes [381]
      Alkynes [383]
      Alcohols [383]
    7.2.3. Carboxylation of Saturated Hydrocarbons [384]
    7.2.4. Practical Applications [384]
      Neocarboxylic Acids [384]
      Hydrocarboxymethylation of Long-Chain Alkenes [385]
      Propionic Acid [385]
      Acrylic Acid and Acrylates [385]
      Acetic Acid [386]
      Dimethyl Carbonate [386]
  7.3. Aminomethylation [386]
  7.4. Recent Developments [387]
    7.4.1. Hydroformylation [387]
      Alkynes [389]
      Asymmetric Hydroformylation [390]
    7.4.2. Formylation of Alkanes [390]
    7.4.3. Carboxylation [391]
      Alkenes and Alkynes [391]
      Alkanes [392]
    7.4.4. Aminomethylation [394]
      References [395]
8. Acylation [407]
  8.1. Acylation of Aromatics [407]
    8.1.1. General Characteristics [407]
    8.1.2. Catalysts and Reaction Conditions [409]
    8.1.3. Recent Developments [410]
      New Soluble Catalysts [410]
      Solid Catalysts [412]
  8.2. Related Acylations [413]
    8.2.1. Formylation [413]
      The Gattermann—Koch Reaction [413]
      The Gattermann Reaction [415]
      Other Formylations [416]
    8.2.2. The Houben-Hoesch Synthesis [417]
  8.3. Acylation of Aliphatic Compounds [417]
    8.3.1. Acylation of Alkenes [418]
    8.3.2. Acylation of Alkynes [420]
    8.3.3. Acylation of Alkanes [421]
      References [422]
9. Oxidation-Oxygenation [427]
  9.1. Oxidation of Alkanes [427]
    9.1.1. Oxidation to Alcohols and Carbonyl Compounds [427]
      Autoxidation of Alkanes [427]
      Oxidation of Methane [429]
      Oxidation of Other Saturated Hydrocarbons [434]
    9.1.2. Oxidations Resulting in Carbon-Carbon Bond Cleavage [444]
      Metal Oxidants [444]
      Electrophilic Reagents [445]
      Oxygenolysis [449]
  9.2. Oxidation of Alkenes [449]
    9.2.1. Epoxidation [449]
      Direct Oxidation with Stoichiometric Oxidants [449]
      Metal-Catalyzed Epoxidation [454]
      Epoxidations Catalyzed by Metalloporphyrins [458]
      Asymmetric Epoxidation [460]
    9.2.2. Reactions with Molecular Oxygen [461]
      Autoxidation [461]
      Reactions with Singlet Oxygen [462]
    9.2.3. Bis-hydroxylation [467]
    9.2.4. Vinylic Oxidation [470]
      Oxidation to Carbonyl Compounds [471]
      Vinylic Acetoxylation [475]
    9.2.5. Oxidative Cleavage [477]
      Ozonation [477]
      Other Oxidants [482]
    9.2.6. Allylic Oxidation [483]
      Allylic Hydroxylation and Acyloxylation [484]
      Oxidation to (?), (?)-Unsaturated Carbonyl Compounds [487]
  9.3. Oxidation of Alkynes [488]
    9.3.1. Oxidation to Carbonyl Compounds [488]
    9.3.2. Oxidative Cleavage [490]
  9.4. Oxidation of Aromatics [491]
    9.4.1. Ring Oxygenation [491]
      Oxidation to Phenols [491]
      Ring Acyloxylation [495]
      Oxidation to Quinones [496]
      Oxidation to Arene Oxides and Arene Diols [497]
      Oxidation with Singlet Oxygen [498]
    9.4.2. Oxidative Ring Cleavage [499]
    9.4.3. Benzylic Oxidation [500]
      Oxidation of Methyl-Substituted Aromatics [500]
      Oxidation of Other Arenes [502]
      Benzylic Acetoxylation [503]
  9.5. Practical Applications [504]
    9.5.1. Oxidation of Alkanes [504]
      Acetic Acid [504]
      Oxidation of Cyclohexane [505]
      Oxidation of Cyclododecane [505]
      sec-Alcohols [506]
    9.5.2. Oxygenation of Alkenes and Dienes [506]
      Ethylene Oxide [506]
      Propylene Oxide [508]
      Acetaldehyde and Acetone [509]
      Vinyl Acetate [509]
      1,4-Diacetoxy-2-butene [510]
      Acrolein and Acrylic Acid [510]
      Methacrolein and Methacrylic Acid [511]
    9.5.3. Ammoxidation [511]
      Acrylonitrile [511 Other Processes [512]
    9.5.4. Oxidation of Arenes [513]
      Phenol and Acetone [513]
      Benzole Acid [514]
      Terephthalic Acid [514]
      Maleic Anhydride [515]
      Phthalic Anhydride [517]
      Anthraquinone [519]
  9.6. Recent Developments [519]
    9.6.1. Oxidation of Alkanes [519]
      Oxidation of Methane [519]
      Oxidation of Higher Alkanes [520]
      Oxidations Relevant to Industrial Processes [522]
    9.6.2. Oxidation of Alkenes [522]
      Epoxidation [522]
      Bis-hydroxylation [526]
      Vinylic Oxidation [526]
      Oxidative Cleavage [527]
      Allylic Oxidation [528]
    9.6.3. Oxidation of Alkynes [528]
    9.6.4. Oxidation of Aromatics [528]
      Ring Oxygenation [528]
      Benzylic Oxidation [529]
    9.6.5. Ammoxidation [529]
      References [530]
10. Heterosubstitution [576]
  10.1. Electrophilic (Acid-Catalyzed) Substitution [577]
    10.1.1. Substitution of Alkanes [577]
      Halogenation [577]
      Nitration [578]
      Sulfuration [579]
    10.1.2. Substitution of Aromatic Hydrocarbons [579]
      Halogenation [580]
      Nitration [581]
      Sulfonation [583]
    10.1.3. Practical Applications [584]
      Chlorobenzene [584]
      Nitration of Benzene and Toluene [584]
      Sulfonation of Benzene and Alkylbenzenes [584]
  10.2. Free-Radical Substitution [585]
    10.2.1. Halogenation of Alkanes and Arylalkanes [585]
      Chlorination of Alkanes [586]
      Fluorination of Alkanes [588]
      Side-Chain Chlorination of Arylalkanes [589]
    10.2.2. Allylic Chlorination [590]
    10.2.3. Sulfochlorination [590]
    10.2.4. Nitration [590]
    10.2.5. Practical Applications [592]
      Chlorination of Alkanes [592]
      Side-Chain Chlorination of Toluene [594]
      Allyl Chloride [594]
      Sulfochlorination of Alkanes [594]
      Nitroalkanes [594]
  10.3. Amination [595]
  10.4. Heterosubstitution through Organometallics [596]
    10.4.1. Transition Metals [596]
    10.4.2. Alkali Metals and Magnesium [598]
  10.5. Recent Developments [600]
    10.5.1. Electrophilic (Acid-Catalyzed) Substitution [600]
      Alkanes [600]
      Aromatics [600]
    10.5.2. Free-Radical Substitution [603]
      Alkanes [603]
      Alkenes [605]
    10.5.3. Amination [606]
    10.5.4. Heterosubstitution through Organometallics [606]
      References [607]
11. Reduction-Hydrogenation [619]
  11.1. Heterogeneous Catalytic Hydrogenation [620]
    11.1.1. Catalysts [620]
    11.1.2. Hydrogenation of Alkenes [620]
      Mechanism [621]
      Stereochemistry [623]
    11.1.3. Hydrogenation of Dienes [625]
    11.1.4. Transfer Hydrogenation [627]
    11.1.5. Hydrogenation of Alkynes [628]
    11.1.6. Hydrogenation of Aromatics [629]
  11.2. Homogeneous Catalytic Hydrogenation [633]
    11.2.1. Catalysts [633]
    11.2.2. Hydrogenation of Alkenes and Dienes [634]
      Mechanism [634]
      Selectivity and Stereochemistry [636]
      Asymmetric Hydrogenation [639]
    11.2.3. Hydrogenation of Alkynes [640]
    11.2.4. Hydrogenation of Aromatics [641]
  11.3. Chemical and Electrochemical Reduction [644]
    11.3.1. Reduction of Alkenes [644]
    11.3.2. Reduction of Alkynes [646]
    11.3.3. Reduction of Aromatics [647]
      Mechanism [648]
      Selectivity [648]
  11.4. Ionic Hydrogenation [650]
    11.4.1. Hydrogenation of Alkenes and Dienes [651]
    11.4.2. Hydrogenation of Aromatics [654]
  11.5. Hydrogenolysis of Saturated Hydrocarbons [655]
    11.5.1. Metal-Catalyzed Hydrogenoly sis [655]
    11.5.2. Ionic Hydrogenolysis [662]
  11.6. Practical Applications [664]
    11.6.1. Selective Hydrogenation of Petroleum Refining Streams [664]
      C(?) Hydrorefining [664
      C(?) Hydrorefining [664]
      C(?) Hydrorefining [664]
      Gasoline Hydrorefining [665]
    11.6.2. Cyclohexane [665]
    11.6.3. Various Нуdrogenations [666]
  11.7. Recent Developments [667]
    11.7.1. Heterogeneous Catalytic Hydrogenation [667]
      Alkenes [667]
      Dienes and Alkynes [669]
      Aromatics [671]
    11.7.2. Homogeneous Catalytic Hydrogenation [672]
      Alkenes and Dienes [672]
      Alkynes [674]
      Aromatics [674]
    11.7.3. Chemical and Electrochemical Hydrogenation [676]
    11.7.4. Ionic Hydrogenation [677]
    11.7.5. Hydrogenolysis of Saturated Hydrocarbons [677]
      References [679]
12. Metathesis [696]
  12.1. Acyclic Alkenes [698]
  12.2. Ring-Opening Metathesis Polymerization [706]
  12.3. Practical Applications [708]
  12.4. Recent Developments [711]
    12.4.1. New Catalysts and Mechanistic Studies [711]
    12.4.2. Metathesis of Alkynes [713]
    12.4.3. Ring-Closing Metathesis [713]
    12.4.4. Ring-Opening Metathesis [714]
    12.4.5. Practical Applications [714]
      References [715]
13. Oligomerization and Polymerization [723]
  13.1. Oligomerization [723]
    13.1.1. Acid-Catalyzed Oligomerization [723]
      Practical Applications [726]
    13.1.2. Base-Catalyzed Oligomerization [727]
    13.1.3. Metal-Catalyzed Oligomerization [728]
      Cyclooligomerization [729]
      Practical Applications [731]
  13.2. Polymerization [734]
    13.2.1. Cationic Polymerization [734]
    13.2.2. Anionic Polymerization [740]
    13.2.3. Free-Radical Polymerization [743]
    13.2.4. Coordination Polymerization [749]
      Catalysts [750]
      Active Centers and Mechanisms [753]
      Stereoregular Polymerization of Propylene [758]
      Isospecific Polymerization [759]
      Syndiospecific Polymerization [764]
      Stereoregular Polymerization of Dienes [765]
    13.2.5. Conducting Polymers [767]
    13.2.6. Practical Applications [770]
      Ethylene Polymers [770]
      Polypropylene [773]
      Polybutylenes [773]
      Styrene Polymers [774]
      Polydienes [775]
  13.3. Recent Developments [776]
    13.3.1. Oligomerization [776]
    13.3.2. Polymerization [778]
      Group IV Metallocene Catalysts [779]
      Late-Transition-Metal Catalysts [782]
      Other Developments [783]
      References [784]
14. Emerging Areas and Trends [807]
  14.1. Green Chemistry [807]
    14.1.1. Chemistry in Nontraditional Reaction Media [808]
      Water [808]
      Fluorous Solvents [809]
      Ionic Liquids [809]
      Supercritical Solvents [810]
    14.1.2. New Catalyst Immobilization or Recovery Strategies [811]
    14.1.3. New Catalysts and Catalytic Processes [814]
  14.2. Carbon Dioxide Recycling to Hydrocarbons [817]
      References [818]
Index [827]
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