Petroleum hydrocarbons, pyrolysis

Dente and Ranzi (in Albright et al., eds.. Pyrolysis Theory and Industrial Practice, Academic Press, 1983, pp. 133-175) Mathematical modehng of hydrocarbon pyrolysis reactions Shah and Sharma (in Carberry and Varma, eds.. Chemical Reaction and Reaction Engineering Handbook, Dekker, 1987, pp. 713-721) Hydroxylamine phosphate manufacture in a slurry reactor Some aspects of a kinetic model of methanol synthesis are described in the first example, which is followed by a second example that describes coping with the multiphcity of reactants and reactions of some petroleum conversion processes. Then two somewhat simph-fied industrial examples are worked out in detail mild thermal cracking and production of styrene. Even these calculations are impractical without a computer. The basic data and mathematics and some of the results are presented. 

Twenty-five years ago the only oxygenated aliphatics produced in important quantities were ethyl and n-butyl alcohols and acetone made by the fermentation of molasses and grain, glycerol made from fats and oils, and methanol and acetic acid made by the pyrolysis of wood. In 1927 the production of acetic acid (from acetylene) and methanol (from synthesis gas) was begun, both made fundamentally from coal. All these oxygenated products are still made from the old raw materials by the same or similar processes, but the amount so made has changed very little in the past quarter century. Nearly all the tremendous growth in the production of this class of compounds has come from petroleum hydrocarbons. 

Butadiene was first produced in the late nineteenth century by pyrolysis of petroleum hydrocarbons (Kirshenbaiun, 1978). Commercial production started in the 1930s. 

Pyrolysis. One type of thermal dissociation a reaction in which complex molecules (as of a heavy petroleum hydrocarbon) split into relatively simple fragments under the application of heat. 

Secondary Reactions of Olefins in Pyrolysis of Petroleum Hydrocarbons... 

A narrow view of this mission would include only the use of analytical pyrolysis techniques (e.g., pyrolysis-mass spectrometry (Py-MS) and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS)) to identify and measure contaminants in samples of outdoor air, soils, sediments, water, and biota. In order to include interesting and useful applications of analytical pyrolysis techniques that otherwise might not be mentioned in the other chapters of this handbook, a broader view of environmental applications will be used to include such topics as the use of analytical pyrolysis to gain an understanding of natural enviromnental processes, such as the conversion of plant materials into soil, coal, and petroleum hydrocarbons. This subject was included in a recent review paper describing the use of analytical pyrolysis for environmental research. Several other review papers contain references pertinent to environmental analysis. ... 

Sakai, T., et al. A Kinetic Study on the Formation of Aromatics During Pyrolysis of Petroleum Hydrocarbons, in Albright, L. F. und Crynes, B. L. Industrial and Laboratory Pyrolyses. ACS Symposion Series 32, Washington 1976, p. 152-177. 

Pyrolysis furnace temperature zones for light liquid petroleum hydrocarbons should be variable as follows ... 

The pattern of commercial production of 1,3-butadiene parallels the overall development of the petrochemical industry. Since its discovery via pyrolysis of various organic materials, butadiene has been manufactured from acetylene as weU as ethanol, both via butanediols (1,3- and 1,4-) as intermediates (see Acetylene-DERIVED chemicals). On a global basis, the importance of these processes has decreased substantially because of the increasing production of butadiene from petroleum sources. China and India stiU convert ethanol to butadiene using the two-step process while Poland and the former USSR use a one-step process (229,230). In the past butadiene also was produced by the dehydrogenation of / -butane and oxydehydrogenation of / -butenes. However, butadiene is now primarily produced as a by-product in the steam cracking of hydrocarbon streams to produce ethylene. Except under market dislocation situations, butadiene is almost exclusively manufactured by this process in the United States, Western Europe, and Japan. 

Ethyleneamines are used in certain petroleum refining operations as well. Eor example, an EDA solution of sodium 2-aminoethoxide is used to extract thiols from straight-mn petroleum distillates (314) a combination of substituted phenol and AEP are used as an antioxidant to control fouling during processing of a hydrocarbon (315) AEP is used to separate alkenes from thermally cracked petroleum products (316) and TEPA is used to separate carbon disulfide from a pyrolysis fraction from ethylene production (317). EDA and DETA are used in the preparation and reprocessing of certain... 

Separation of raw feedstock. The pyrolysis of petroleum feedstream is carried out at 650-900°C at normal pressure in the presence of steam. The so-called steam-cracking process involves carbon-carbon splitting of saturated, unsaturated and aromatic molecules. The following steam-cracker fractions are used as raw materials to produce hydrocarbon resins. 

Enciforming [National Chemical reforming] A petroleum reforming process that converts pyrolysis gasoline to mixtures of propane, butane, and aromatic hydrocarbons, thereby obviating the usual hydrogenation and solvent extraction processes. The catalyst is a ZSM-5-type zeolite containing both iron and a platinum metal. Developed by the National Chemical Laboratory, Pune, India, since 1988, but not yet commercialized. 

Another aspect to be described by example is hydrothermal petroleum and the related high temperature alteration of natural products in aqueous medium. In such cases immature organic detritus with natural products is altered mainly to hydrocarbons by rapid reductive hydrous pyrolysis. 

Mixtures of gaseous or liquid hydrocarbons which can be vaporized represent the raw materials preferable for the industrial production of carbon black. Since aliphatic hydrocarbons give lower yields than aromatic hydrocarbons, the latter are primarily used. The best yields are given by unsubstituted polynuclear compounds with 3-4 rings. Certain fractions of coal tar oils and petrochemical oils from petroleum refinement or the production of ethylene from naphtha (aromatic concentrates and pyrolysis oils) are materials rich in these compounds. These aromatic oils, which are mixtures of a variety of substances, are the most important feedstocks today. Oil on a petrochemical basis is predominant. A typical petrochemical oil consists of 10-15% monocyclic, 50-60% bicyclic, 25-35% tricyclic, and 5-10% tetracyclic aroma tes. 

Dr. Friedel. No. Products of the pyrolysis of coal under high temperature carbonization conditions surely must arise from degradation. The quantitative prediction of C7 alkane isomers from coal may possibly indicate a relationship in compositions of coal and petroleum. The hydrocarbons from each perhaps should be similar since both are supposedly derived from organic plants ... 

Mos of the solid carbonaceous material available to industry is derived from the pyrolysis of petroleum residues, coal, and coal tar residues. Understanding the reactions occurring during pyrolysis would be beneficial in conducting materials research on the manufacture of carbonaceous products. The pyrolysis of aromatic hydrocarbons has been reported to involve condensation and polymerization reactions that produce complex carbonaceous materials (I). Interest in the mechanism of pyrolysis of aromatic compounds is evidenced in a recent study by Edstrom and Lewis (2) on the differential thermal analysis of 84 model aromatic hydrocarbons. The study demonstrated that carbon formation was related to the molecular size of the compound and to energetic factors that could be estimated from ionization potentials. 

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