Pyrolysis, high-temperature

Polysaccharide pyrolysis at 375-520°C is accompanied by a higher rate of weight loss and evolution of a complex mixture of vapor-phase compounds preponderantly of HsO, CO, C02, levoglucosan, furans, lactones, and phenols (Shafizadeh, 1968). The volatile and involatile phase compositions are conditional on the rate of removal of the vapor phase from the heated chamber (Irwin, 1979), inasmuch as the primary decomposition products are themselves secondary reactants. The reaction kinetics is described as pseudo zero order (Tang and Neill, 1964) and zero order initially, followed by pseudo first order and first order (Lipska and Parker, 1966), suggesting an 

The flammability of the vapor phase of cellulose apparels gave special urgency to a search for ways to lower the combustion temperatures (lower Ea) and increase the rate of weight loss by using flame retardants, thereby rapidly augmenting the rapid accumulation of nonflammable gases at the expense of combustible distillate (Shafizadeh, 1968). 

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In contrast, the ultrasonic irradiation of organic Hquids has been less studied. SusHck and co-workers estabHshed that virtually all organic Hquids wiU generate free radicals upon ultrasonic irradiation, as long as the total vapor pressure is low enough to allow effective bubble coUapse (49). The sonolysis of simple hydrocarbons (for example, alkanes) creates the same kinds of products associated with very high temperature pyrolysis (50). Most of these products (H2, CH4, and the smaller 1-alkenes) derive from a weU-understood radical chain mechanism. 

Hoechst HTP Process. The two-stage HTP (high temperature pyrolysis) process was operated by Farbwerke Hoechst ia Germany. The cracking stock for the HTP process can be any suitable hydrocarbon. With hydrocarbons higher than methane, the ratio of acetylene to ethylene can be varied over a range of 70 30 to 30 70. Total acetylene and ethylene yields, as wt % of the feed, are noted ia Table 11. 

Table 11. High Temperature Pyrolysis Process Yields...

Ammonia is used in the fibers and plastic industry as the source of nitrogen for the production of caprolactam, the monomer for nylon 6. Oxidation of propylene with ammonia gives acrylonitrile (qv), used for the manufacture of acryHc fibers, resins, and elastomers. Hexamethylenetetramine (HMTA), produced from ammonia and formaldehyde, is used in the manufacture of phenoHc thermosetting resins (see Phenolic resins). Toluene 2,4-cHisocyanate (TDI), employed in the production of polyurethane foam, indirectly consumes ammonia because nitric acid is a raw material in the TDI manufacturing process (see Amines Isocyanates). Urea, which is produced from ammonia, is used in the manufacture of urea—formaldehyde synthetic resins (see Amino resins). Melamine is produced by polymerization of dicyanodiamine and high pressure, high temperature pyrolysis of urea, both in the presence of ammonia (see Cyanamides). 

Biomedical. Heart-valve parts are fabricated from pyrolytic carbon, which is compatible with living tissue. Such parts are produced by high temperature pyrolysis of gases such as methane. Other potential biomedical apphcations are dental implants and other prostheses where a seal between the implant and the living biological surface is essential. Plasma and arc-wire sprayed coatings are used on prosthetic devices, eg, hip implants, to achieve better bone/tissue attachments (see Prosthetic and BiOLffiDiCALdevices). 

Outside the realm of typical hydrocarbon pyrolysis is the high temperature pyrolysis of methane. In one variant of this process, which has only been commercialized to produce acetylene (with some BTX), methane reacts in an electric arc at about 1500°C (17) with very short contact times. At higher temperatures or with a catalyst and added hydrogen, BTX is produced with fairly high selectivity (18). 

The high temperature pyrolysis of sulfonyl fluonde results in the elimination of sulfur dioxide, although secondary reactions also occur, depending on the residence tune With perfluorooctanesulfonyl fluonde, long residence times result in perfluoro(Cg-Cig) compounds, and shorter residence times lead to perfluoro-hexadecane [98] (equation 65)... 

Carbon-Fiber Electrodes The growing interest in ultramicroelectrodes (Section 4-5.4) has led to widespread use of carbon fibers in electroanalysis. Such materials are produced, mainly in connection with the preparation of high-strength composites, by high-temperature pyrolysis of polymer textiles or via... 

Only two processes, high-temperature pyrolysis and mobile incineration, have proved effective for soil decontamination and are considered to be commercially viable. Both involve heating the contaminated soil to a high temperatnre, which is costly in terms of energy use and materials handling. There are substantial opportunities for innovation and development of processes for the separation of eontaminants from soils and the in-situ treatment of contaminated soils. Examples of each are given in the following subsections. 

A pilot plant for the high temperature pyrolysis of polymers to recycle plastic waste to valuable products based on rotating cone reactor (RCR) technology. The RCR used in this pilot plant, the continuous RCR was an improved version of the bench-scale RCR previously used for the pyrolysis of biomass, PE and PP. 9 refs. 

Industrial Engineering Chemistry Research 37, No.6, June 1998, p.2293-300 RECYCLING OF POLYETHENE AND POLYPROPENE IN A NOVEL BENCH-SCALE ROTATING CONE REACTOR BY HIGH-TEMPERATURE PYROLYSIS Westerhout R W J Waanders J Kuipers JAM van Swaaij W P M Twente,University... 

The high temperature pyrolysis of PE, PP and mixtures of these polymers was studied in a novel bench-scale rotating eone reaetor to identify the optimal operating eonditions for this reaetor. It was shown that the effect of the sand or reaetor temperature on the product spectrum obtained was large eompared with the effect of other parameters, e.g. residenee time. 15 refs. 

Dodolet JP, Cote R, Faubert G, Denes G, Guay D, Bertrand P (1998) Iron catalysts prepared by high-temperature pyrolysis of tetraphenylporphyrins adsorbed on carbon black for oxygen reduction in polymer electrolyte fuel cells. Electrochim Acta 43 341-353... 

It is now clearly demonstrated through the use of free radical traps that all organic liquids will undergo cavitation and generate bond homolysis, if the ambient temperature is sufficiently low (i.e., in order to reduce the solvent system s vapor pressure) (89,90,161,162). The sonolysis of alkanes is quite similar to very high temperature pyrolysis, yielding the products expected (H2, CH4, 1-alkenes, and acetylene) from the well-understood Rice radical chain mechanism (89). Other recent reports compare the sonolysis and pyrolysis of biacetyl (which gives primarily acetone) (163) and the sonolysis and radiolysis of menthone (164). Nonaqueous chemistry can be complex, however, as in the tarry polymerization of several substituted benzenes (165). 

Cyclic gas generators converted coke, a by-product of high-temperature pyrolysis process, to a synthetic gas by alternatively exposing the coke to air to provide heat and to steam to produce a gas that burned with a blue flame. The coal gas was know as blue water gas (Probstein, R. F. and Hicks, R. E., Synthetic Fuels, McGraw-Hill, 1982, p. 7). 

The second observation is that discrete absorptions decline in intensity as the pyrolysis progresses and disappear near 700°C (the same trend is found with other carbons). It appears that no spectroscopically observable species remain after the high temperature pyrolysis or degassing. Some species, however, can be re-established [1 6]. ... 

H. R. Linden High temperature pyrolysis of coal with high energy sources seems to follow readily predictable paths similar to hydrocarbon pyrolysis. The effects of pressure, gas atmosphere, reaction time, and the volatile matter" content of the coal bear the same relationship to yields of methane, ethane, ethylene, acetylene, and hydrogen as for simple hydrocarbons. Effective reaction temperature, although not directly measurable, could be estimated by means of a suitable chemical thermometer, such as the C-. H-. -C. H4-H. system which approaches equilibrium very rapidly. As Dr. Given also noted, equating the volatile matter" to the reactive portion of the coal is an oversimplification but adequate for empirical purposes the C H ratio of the coal would probably be more suitable. 

Some unusual flow reactors are shown in Figure 17.14. The residence times in the units for high temperature pyrolysis to make acetylene and ethylene and for the oxidation of ammonia are measured in fractions of a second acetic anhydride is made by mixing reactants quickly in a centrifugal pump NO is formed at very high temperature in an electric furnace and ethylene is polymerized at high or low pressures in the two units shown. 

Figure 17.23. Representative temperature profiles in reaction systems (see also Figs. 17.20, 17.21(d), 17.22(d), 17.30(c), 17.34, and 17.35). (a) A jacketed tubular reactor, (b) Burner and reactor for high temperature pyrolysis of hydrocarbons (Ullmann, 1973, Vol. 3, p. 355) (c) A catalytic reactor system in which the feed is preheated to starting temperature and product is properly adjusted exo- and endothermic profiles, (d) Reactor with built-in heat exchange between feed and product and with external temperature adjustment exo- and endothermic profiles.

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