Pyrolysis controlled

Electron-deficient alkenes add stereospecifically to 4-hydroxy-THISs with formation of endo-cycloadducts. Only with methylvinyl-ketone considerable amounts of the exo isomer are produced (Scheme 8) (16). The adducts (6) may extrude hydrogen sulfide on heating with methoxide producing 2-pyridones. The base is unnecessary with fumaronitrile adducts. The alternative elimination of isocyanate Or sulfur may be controlled using 7 as the dipolarenOphile. The cycloaddition produces two products, 8a (R = H, R = COOMe) and 8b (R = COOMe, R =H) (Scheme 9) (17). Pyrolysis of 8b leads to extrusion of furan and isocyanate to give a thiophene. The alternative S-elimi-nation can be effected by oxidation of the adduct and subsequent pyrolysis. 

Manufacture. For the commercial production of DPXN (di-/)-xylylene) (3), two principal synthetic routes have been used the direct pyrolysis of -xylene (4, X = Y = H) and the 1,6-Hofmaim elimination of ammonium (HNR3 ) from a quaternary ammonium hydroxide (4, X = H, Y = NR3 ). Most of the routes to DPX share a common strategy PX is generated at a controlled rate in a dilute medium, so that its conversion to dimer is favored over the conversion to polymer. The polymer by-product is of no value because it can neither be recycled nor processed into a commercially useful form. Its formation is minimised by careful attention to process engineering. The chemistry of the direct pyrolysis route is shown in equation 1 ... 

DPXC ndDPXD. The economic pressure to control dimer costs has had an important effect on what is in use today (ca 1997). Attaching substituents to the ring positions of a [2.2]paracyclophane does not proceed with isomeric exclusivity. Indeed, isomeric purity in the dimer is not an essential requirement for the obtaining of isomeric purity, eg, monosubstituted monomer, in the pyrolysis. Any mixture of the four possible heteronucleady disubstituted dichloro[2.2]paracyclophanes, will, after all, if pyrolyzed produce the same monomer molecule, chloro- -xyljIene [10366-09-3] (16) (Fig. 4). 

Thermal Stability. The saturated C —C 2 ketones are thermally stable up to pyrolysis temperatures (500—700°C). At these high temperatures, decomposition can be controlled to produce useful ketene derivatives. Ketene itself is produced commercially by pyrolysis of acetone at temperatures just below 550°C (see Ketenes, ketene dil rs, and related substances). 

Kutrieb Corporation (Chetek, Wisconsin) operates a pyrolator process for converting tires into oil, pyrolytic filler, gas, and steel. Nu-Tech (Bensenvike, Illinois) employs the Pyro-Matic resource recovery system for tire pyrolysis, which consists of a shredding operation, storage hopper, char-coUection chambers, furnace box with a 61-cm reactor chamber, material-feed conveyor, control-feed inlet, and oil collection system. It is rated to produce 272.5 L oil and 363 kg carbon black from 907 kg of shredded tires. TecSon Corporation (Janesville, Wisconsin) has a Pyro-Mass recovery system that pyroly2es chopped tire particles into char, oil, and gas. The system can process up to 1000 kg/h and produce 1.25 MW/h (16). 

Other techniques include oxidative, steam atmosphere (33), and molten salt (34) pyrolyses. In a partial-air atmosphere, mbber pyrolysis is an exothermic reaction. The reaction rate and ratio of pyrolytic filler to ok products are controlled by the oxygen flow rate. Pyrolysis in a steam atmosphere gives a cleaner char with a greater surface area than char pyroly2ed in an inert atmosphere however, the physical properties of the cured compounded mbber are inferior. Because of the greater surface area, this pyrolytic filler could be used as activated carbon, but production costs are prohibitive. Molten salt baths produce pyroly2ed char and ok products from tine chips. The product characteristics and quantities depend on the salt used. Recovery of char from the molten salt is difficult. 

Chlorinated by-products of ethylene oxychlorination typically include 1,1,2-trichloroethane chloral [75-87-6] (trichloroacetaldehyde) trichloroethylene [7901-6]-, 1,1-dichloroethane cis- and /n j -l,2-dichloroethylenes [156-59-2 and 156-60-5]-, 1,1-dichloroethylene [75-35-4] (vinyhdene chloride) 2-chloroethanol [107-07-3]-, ethyl chloride vinyl chloride mono-, di-, tri-, and tetrachloromethanes (methyl chloride [74-87-3], methylene chloride [75-09-2], chloroform, and carbon tetrachloride [56-23-5])-, and higher boiling compounds. The production of these compounds should be minimized to lower raw material costs, lessen the task of EDC purification, prevent fouling in the pyrolysis reactor, and minimize by-product handling and disposal. Of particular concern is chloral, because it polymerizes in the presence of strong acids. Chloral must be removed to prevent the formation of soflds which can foul and clog operating lines and controls (78). 

Carbon Composites. Cermet friction materials tend to be heavy, thus making the brake system less energy-efficient. Compared with cermets, carbon (or graphite) is a thermally stable material of low density and reasonably high specific heat. A combination of these properties makes carbon attractive as a brake material and several companies are manufacturing carbon fiber—reinforced carbon-matrix composites, which ate used primarily for aircraft brakes and race cats (16). Carbon composites usually consist of three types of carbon carbon in the fibrous form (see Carbon fibers), carbon resulting from the controlled pyrolysis of the resin (usually phenoHc-based), and carbon from chemical vapor deposition (CVD) filling the pores (16). 

Manufacture. Dicyandiamide is converted into melamine by heating. Simple pyrolysis above the melting point leads to an exothermic reaction however, deammoniation occurs, forming products containing two or three triazine rings as well as melamine. After it was discovered in 1940 that deammoniation can be counteracted by conducting the reaction under ammonia pressure, various methods were developed to control the exothermic reaction on an industrial scale. 

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... 

Has, Uwe. Sensor Controlled Pyrolysis in Con.surner Ovens. Sensor llevieiv US i J998), pp. 18.8.192. 

As can be noted in Figure 21.7.2, steam and ediane are mi.xed before entering die reactor tubes where pyrolysis reacdons take place. All feed and product lines must be equipped with appropriate control devices to ensure safe operation. The FTA flow chart breaks down a TOP event (see descripdon of fault tree in Unit II) into all possible basic causes. Aldiough, diis mediod is more structured than a PHA, it addresses only one individual event at a dine. To use an FTA for a complete liazard analysis, all possible TOP events must be identified and investigated this would be extremely time consuming and perhaps urmecessary in a preliminary design. 

Early attempts to prepare 5-amino- and 5-acylaminobenzofuroxans by hypochlorite oxidation of the corresponding o-nitroanilines met with failure. Pyrolysis of the appropriate azide, however, gives 5-dimetliylamino- and 5-acetamidobenzofuroxan, whereas urethans of type (33) are produced by Curtius degradation of the 5-carboxylic acid. Controlled hydrolysis of the acetamido compound and the... 

Carbon fibers are special reinforcement types having a carbon content of 92-99 wt%. They are prepared by controlled pyrolysis of organic materials in fibrous forms at temperatures ranging from 1,000-3,000°C. 

Analyses of rate measurements for the decomposition of a large number of basic halides of Cd, Cu and Zn did not always identify obedience to a single kinetic expression [623—625], though in many instances a satisfactory fit to the first-order equation was found. Observations for the pyrolysis of lead salts were interpreted as indications of diffusion control. More recent work [625] has been concerned with the double salts jcM(OH)2 yMeCl2 where M is Cd or Cu and Me is Ca, Cd, Co, Cu, Mg, Mn, Ni or Zn. In the M = Cd series, with the single exception of the zinc salt, reaction was dehydroxylation with concomitant metathesis and the first-order equation was obeyed. Copper (=M) salts underwent a similar change but kinetic characteristics were more diverse and examples of obedience to the first order, the phase boundary and the Avrami—Erofe ev equations [eqns. (7) and (6)] were found for salts containing the various cations (=Me). 

Kinetic observations for decomposition of some representative transition metal sulphides are summarized in Table 13. Several instances of an advancing interface [contracting volume, eqn. (7), n = 3] rate process have been identified and the rate may be diminished by the presence of sulphur. Diffusion control is, however, believed to be important in the reactions of two lower sulphides (Ni0.9sS. [687] and Cu1-8S [688]). These solids have attracted particular interest since both are commercially valuable ores and pyrolysis constitutes one possible initial step in metal extraction. 

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). 

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