Pyrolysis product

Pyrolysis of food samples provides a large number of products, which, after detection by MS and analysis by advanced statistical treatment, can be used to compare different samples. The method is very rapid and does not require chromatographic separation or MS identification of the pyrolysis products. Pyrolysis MS, coupled with multivariate data analysis procedures, has been used to discriminate between cocoa butters of three different continental areas (Radovic et al., 1998). The technique could in some cases separate deodorized from non-deodorized cocoa butters and also show those that have had alkali treatment. The presence of non-cocoa fats did not affect the assay. 

At pyrolysis temperatures (e.g., 800-1,200 °C) waste rubber (usually tyres that are either whole or shredded) can be reduced down to gas, oil, char, metal and inorganic fractions that, with further processing, can then be used as energy sources, or additives and starting materials for other products. 

An illustration of the products present in the gas, oil and char fractions resulting from the pyrolysis of a styrene-butadiene rubber (SBR) tyre is presented in the following [2]  

Char fraction - 33-35% ( 3-5% sulfur) carbon and inorganic ash (mostly zinc oxide). 

Carrying out secondary processing steps on these three fractions enables them to be converted into value-added products. For example, once purified, the pyro-gas fraction can be used as an energy source to help run the pyrolysis operation. The oil fraction can be turned into carbon black by a furnace process, or into fuel oil, or chemical feedstock by distillation. The char fraction can be treated to yield products such as activated carbon, recovered carbon black and recovered inorganic compounds. 

It is also possible to recover other important products from waste tyres when they are pyrolysed, one being the steel that goes into their construction. The approximate proportions of steel and other principal products obtained by this route are shown in Table 8.1. 

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Chemical Evidence for PX Monomer. Estabhshing early on that PX is indeed the pyrolysis product, rather than the molecule formed by breaking only one of the original diben2yl bonds, the dimer diradical (5), would prove to be an important development. 

Several commercial polyester fabrics are flame retarded using low levels of phosphoms additives that cause them to melt and drip more readily than fabrics without the flame retardant. This mechanism can be completely defeated by the presence of nonthermoplastic component such as infusible fibers, pigments, or by siUcone oils which can form pyrolysis products capable of impeding melt flow (27,28). 

Physical or chemical vapor-phase mechanisms may be reasonably hypothesized in cases where a phosphoms flame retardant is found to be effective in a noncharring polymer, and especially where the flame retardant or phosphoms-containing breakdown products are capable of being vaporized at the temperature of the pyrolyzing surface. In the engineering of thermoplastic Noryl (General Electric), which consists of a blend of a charrable poly(phenylene oxide) and a poorly charrable polystyrene, experimental evidence indicates that effective flame retardants such as triphenyl phosphate act in the vapor phase to suppress the flammabiUty of the polystyrene pyrolysis products (36). 

Because PTFE resins decompose slowly, they may be heated to a high temperature. The toxicity of the pyrolysis products warrants care where exposure of personnel is likely to occur (120). Above 230°C decomposition rates become measurable (0.0001% per hour). Small amounts of toxic perfiuoroisobutylene have been isolated at 400°C and above free fluorine has never been found. Above 690°C the decomposition products bum but do not support combustion if the heat is removed. Combustion products consist primarily of carbon dioxide, carbon tetrafluoride, and small quantities of toxic and corrosive hydrogen fluoride. The PTFE resins are nonflammable and do not propagate flame. 

The Du Pont HaskeU Laboratory for Toxicology and Industrial Medicine has conducted a study to determine the acute inhalation toxicity of fumes evolved from Tefzel fluoropolymers when heated at elevated temperatures. Rats were exposed to decomposition products of Tefzel for 4 h at various temperatures. The approximate lethal temperature (ALT) for Tefzel resins was deterrnined to be 335—350°C. AH rats survived exposure to pyrolysis products from Tefzel heated to 300°C for this time period. At the ALT level, death was from pulmonary edema carbon monoxide poisoning was probably a contributing factor. Hydrolyzable fluoride was present in the pyrolysis products, with concentration dependent on temperature. 

Chemistry. Coal gasification iavolves the thermal decomposition of coal and the reaction of the carbon ia the coal, and other pyrolysis products with oxygen, water, and hydrogen to produce fuel gases such as methane by internal hydrogen shifts... 

Starved-Air or Partial Combustion. To obtaia the temperatures aeeded for the pyrolysis reactioa to occur, a limited amouat of oxygea is allowed to eater the combustioa zoae. This oxygea reacts with the feed or pyrolysis products and releases the needed energy within the combustor. Both pyrolysis and combustion products are obtained. The products leaving the system contain a large amount of chemical energy. 

From the time that isoprene was isolated from the pyrolysis products of natural mbber (1), scientific researchers have been attempting to reverse the process. In 1879, Bouchardat prepared a synthetic mbbery product by treating isoprene with hydrochloric acid (2). It was not until 1954—1955 that methods were found to prepare a high i i -polyisoprene which dupHcates the stmcture of natural mbber. In one method (3,4) a Ziegler-type catalyst of tri alkyl aluminum and titanium tetrachloride was used to polymerize isoprene in an air-free, moisture-free hydrocarbon solvent to an all i7j -l,4-polyisoprene. A polyisoprene with 90% 1,4-units was synthesized with lithium catalysts as early as 1949 (5). 

Itaconic 2Lcid[97-65-4] (methylenebutanedioic acid, methylenesuccinic acid) is a crystaUine, high, melting acid (mp = 167-168) produced commercially by fermentation of carbohydrates (1 4). Itaconic acid is produced in the broth from citric acid (qv). Isolated from the pyrolysis products of citric acid in 1836, this a-substituted acryUc acid received its name by rearrangement of aconitic, the acid from which it is formed by decarboxylation. 

LLDPE can present a certain health hazard when it bums, since smoke, fumes, and toxic decomposition products are sometimes formed in the process. Exposure to burning LLDPE can cause irritation of the skin, eyes, and mucous membranes of the nose and throat due to the presence of acrolein and formaldehyde (81). Toxicity of LLDPE pyrolysis products depends on temperature, heating rate, and the sample size (82—84). 

American Tire Reclamation, Inc. (Detroit, Michigan) plans to constmct a commercial-size plant to supply a refined version of carbon black and oil produced by pyrolysis of tires. The pyrolysis product improves aging and reduces mtting when added to asphalt (qv) (28). 

Health nd SMety Factors. The lowest pubhshed human oral toxic dose is 430 mg/kg, causing nervous system disturbances and gastrointestinal symptoms. The LD q (rat, oral) is 750 mg/kg (183). Thiocyanates are destroyed readily by soil bacteria and by biological treatment systems in which the organisms become acclimatized to thiocyanate. Pyrolysis products and combustion products can include toxic hydrogen cyanide, hydrogen sulfide, sulfur oxides, and nitrogen oxides. 

Unreacted EDC recovered from the pyrolysis product stream contains a variety of cracking by-products. A number of these, eg, trichloroethylene, chloroprene, and benzene, are not easily removed by simple distillation and require additional treatment (78). Chloroprene can build up in the light ends... 

J. J. Brenden, Effect of Fire-Retardant and Other Inorganic Salts on Pyrolysis Products ofPonderosa Pine at 250° and 350°C, Research Paper PPL 80, U.S. Department of Agriculture, Eorest Service, Eorest Products Laboratory, Madison, Wise., 1967. 

Physical properties of pentachloroethane are Hsted in Table 10. The kinetics and mechanism of the pyrolysis of pentachloroethane in the temperature ranges of 407—430°C and 547—592°C have been studied (133—135). Tetrachloroethylene and hydrogen chloride are the two primary pyrolysis products, showing that dehydrochlorination is the primary reaction. 

Table 3.9 Classes of pyrolysis products produced during fires...

Chemical type involved in a fire Pyrolysis product... 

Fires Pyrolysis products Combustion products Vaporization Through domino effects... 

Rosin core solder, pyrolysis products Rotenone (commercial)... 

Rosin core solder pyrolysis products (as formaldehyde)... 

The analysis of industrial samples such as the pyrolysis products of Turkish lignites has been carried out by using GC, SEC and coupled HPLC/GC (16). The combustion products of lignites result in atmospheric pollution. The pyrolysis of... 

A typical ethane cracker has several identical pyrolysis furnaces in which fresh ethane feed and recycled ethane are cracked with steam as a diluent. Figure 3-12 is a block diagram for ethylene from ethane. The outlet temperature is usually in the 800°C range. The furnace effluent is quenched in a heat exchanger and further cooled by direct contact in a water quench tower where steam is condensed and recycled to the pyrolysis furnace. After the cracked gas is treated to remove acid gases, hydrogen and methane are separated from the pyrolysis products in the demethanizer. The effluent is then treated to remove acetylene, and ethylene is separated from ethane and heavier in the ethylene fractionator. The bottom fraction is separated in the deethanizer into ethane and fraction. Ethane is then recycled to the pyrolysis furnace. 

The first and to date only synthesis of the parent system 2 uses a flash-vacuum pyrolysis (FVP) of 7,8-diazapentacyclo[4.2.2.02-5.03 9.04 10]dec-7-ene (diazabasketene, 1). After condensation at -196 °C, the pyrolysis product is distilled in vacuum to give pure azocine in ca. 60% yield.12... 

V sol in acetic acid, ethanol and w. Prepn is by dehydration of propan-2-ol over Al oxide at 330°. It is also obtd as a pyrolysis product of propane and as a fraction of petr well head gases Propene has a Qc of 460.47kcal/mole the expln limits with air are 2.0 to 11.1% (Ref 2) it has an autoign temp of 927°F. Under unusual conditions, such as 955 atms press and... 

Figure 20, a magnitude schematic view of zone 1 in Fig. 19, depicts this effect. These exothermic oxidative reactions in zone 1 can release sufficient heat to expel partially combusted products, pyrolysis products, and fuel and oxidizer fragments into the gas phase, where they can intermix and burn completely. The maximum flame temperature will then be reached in the luminous zone, where the largest portion of the heat is released. However, a relatively... 

The oxygen index method was used to demonstrate synergy. This method measures ease of ignition, that is the facility with which a material or it s pyrolysis products can be ignited under given conditions of temperature and oxygen concentration. This test is indicative of the intrinsic flamability of a material but... 

Special clean-up procedures were developed for PBDD/F in the pyrolysis products formed in either furnace for incineration products of the VCI oven the following clean-up procedure was developed (ref. 11), see Scheme 1. 

Similar results are obtained from incineration of polymeric materials with octabromo- and pentabromodiphenyl ether (refs. 11,12). The temperature with the maximum PBDF-yield depends on the kind of polymeric matrix. All three bromo ethers 1-2 give the same isomer distribution pattern with preference for tetrabrominated dibenzofiirans. The overall yield of PBDF is lower for incineration of pentabromobiphenyl ether 2, 4 % at 700°C compared to 29 % for ether 1 at 500 °C (ref. 12). The preferred formation of tetrabrominated fiirans observed at all temperatures cannot be a result of thermodynamic control of the cyclisation reaction it is likely due to the special geometry of the furnaces. One explanation is that a spontaneous reaction occurs at approximately 400°C while the pyrolysis products are transferred to the cooler zones of the reactor details can be found elsewhere (ref. 12). 

A novel reactor for pyrolysis of a PE melt stirred by bubbles of flowing nitrogen gas at atmospheric pressure permits uniform temperature depolymerisation. Sweep-gas experiments at temperatures 370-410 C allowed pyrolysis products to be collected separately as reactor residue (solidified PE melt), condensed vapour, and uncondensed gas products. MWDs determined by GPC indicated that random scission and repolymerisation (crosslinking) broadened the polymer-melt MWD. 19 refs. USA... 

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