Pyrolysis temperature

Pyrolysis (Irwin, 1979, 1982 Tomasik et al., 1989b) is the decomposition of a substance at elevated temperatures, principally by dry heat. Low-temperature pyrolysis arbitrarily refers to thermochemical decomposition in the 121.1- 

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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. 

Thermochemical Liquefaction. Most of the research done since 1970 on the direct thermochemical Hquefaction of biomass has been concentrated on the use of various pyrolytic techniques for the production of Hquid fuels and fuel components (96,112,125,166,167). Some of the techniques investigated are entrained-flow pyrolysis, vacuum pyrolysis, rapid and flash pyrolysis, ultrafast pyrolysis in vortex reactors, fluid-bed pyrolysis, low temperature pyrolysis at long reaction times, and updraft fixed-bed pyrolysis. Other research has been done to develop low cost, upgrading methods to convert the complex mixtures formed on pyrolysis of biomass to high quaHty transportation fuels, and to study Hquefaction at high pressures via solvolysis, steam—water treatment, catalytic hydrotreatment, and noncatalytic and catalytic treatment in aqueous systems. 

F. B. Carlson, L. H. Yardumian, and M. T. Atwood, "The TOSCO AT, Process for Low Temperature Pyrolysis of Coal," paper presented at... 

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). 

Reaction Conditions. Typical iadustrial practice of this reaction involves mixing vapor-phase propylene and vapor-phase chlorine in a static mixer, foEowed immediately by passing the admixed reactants into a reactor vessel that operates at 69—240 kPa (10—35 psig) and permits virtual complete chlorine conversion, which requires 1—4 s residence time. The overaE reactions are aE highly exothermic and as the reaction proceeds, usuaEy adiabaticaEy, the temperature rises. OptimaEy, the reaction temperature should not exceed 510°C since, above this temperature, pyrolysis of the chlorinated hydrocarbons results in decreased yield and excessive coke formation (27). 

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. 

Bordeaux, 22nd-23rd Sept. 1993, p.59-64. 627-8(13) LOW TEMPERATURE PYROLYSIS FOR CHEMICAL SEPARATION OF PLASTIC MIXTURES... 

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... 

To use the DCI probe, 1-2 xL of the sample (in solution) are applied to the probe tip, composed of a small platinum coil, and after the solvent has been allowed to evaporate at room temperature, the probe is inserted into the source. DCI probes have the capability of very fast temperature ramping from 20 to 700 °C over several seconds, in order to volatilise the sample before it thermally decomposes. With slower temperature gradients, samples containing a mixture of components can be fractionally desorbed. The temperature ramp can be reproduced accurately. It is important to use as volatile a solvent as possible, so as to minimise the time required to wait for solvent evaporation, which leaves a thin layer of sample covering the coil. The observed spectrum is likely to be the superposition of various phenomena evaporation of the sample with rapid ionisation direct ionisation on the filament surface direct desorption of ions and, at higher temperature, pyrolysis followed by ionisation. 

Thermolysis-mass spectrometry is ideal for examining the amount of residual monomer and processing solvents present in polymers. In thermolysis, the polymer is heated from room temperature to 200-300 °C, and is then often held isothermally in order to drive off volatile components. Low-temperature pyrolysis (350-400 °C) of PP compounds in direct mass-spectral analysis has shown volatiles from PP at every carbon number to masses well above 1000 Da [37]. 

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). 

Figure 1. Initial chemisorption rates (140°C) and pyrolysis weight loss against maximum charring temperature. Pyrolysis at 5°/min in nitrogen. (Reproduced with permission from Ref. 19. Copyright 1989 Elsevier Scientific Publishing Company, Inc.)...

Processes which generate heat in organic materials are reviewed. At ordinary temperatures, respiration of living cells and particularly the metabolism of microorganisms may cause self-heating, while at elevated temperatures pyrolysis, abiotic oxidation, and adsorption of various gases by charred materials drive temperatures up whenever the released heat is unable to dissipate out of the material. The crucial rate of pyrolytic heat release depends on exothermicity and rates of the pyrolysis process. 

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]. ... 

The decomposition of CO has been studied in shock tubes14-16 at temperatures in excess of 6000 °K, and in glass vessels17 at temperatures in the region of 1000 °K. The low-temperature pyrolysis is entirely heterogeneous. Fairbairn s studies14 have shown that the assumption adopted by previous workers that the decomposition is controlled by... 

Whether the reuse of the metals obtained from incineration as a preservative, or some form of permanent immobilization is preferable requires careful thought. Low-temperature pyrolysis has been suggested as an alternative to incineration, since this would be expected to lead to lower losses of metals (Helsen elal., 1998). 

Helsen, L., Van de Bulck, E. and Hery, l.S. (1998). Total recycling of CCA treated wood waste by low-temperature pyrolysis. Waste Management, 18(6-8), 571-578. 

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