Pyrolysis, vacuum

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. 

Homogeneous Pyrolysis Vacuum pyrolysis and pressure pyrolysis are essentially the same operation, but these methods have traditionally been dealt separately due to the design of the laboratory setup. For industrial applications. 

In a world increasingly conscious of the dangers of contact with chemicals, a process that is conducted within the walls of a vacuum chamber, such as the VDP process for parylene coatings, offers great advantages. Provided the vacuum pump exhaust is appropriately vented and suitable caution is observed in cleaning out the cold trap (trace products of the pyrolysis, which may possibly be dangerous, would collect here), the VDP parylene process has an inherently low potential for operator contact with hazardous chemicals. 

Utilisa tion of shale oil products for petrochemical production has been studied (47—51). The effects of prerefining on product yields for steam pyrolysis of shale oil feed and the suitabiUty of Green River shale oil as a petrochemical feedstock were investigated. Pyrolysis was carried out on the whole oil, vacuum distillate, and mildly, moderately, and severely hydrogenated vacuum distillates. 

PhenoHc and furfuryl alcohol resins have a high char strength and penetrate into the fibrous core of the fiber stmcture. The phenoHc resins are low viscosity resoles some have been neutralized and have the salt removed. An autoclave is used to apply the vacuum and pressure required for good impregnation and sufficient heat for a resin cure, eg, at 180°C. The slow pyrolysis of the part foUows temperatures of 730—1000°C are recommended for the best properties. On occasion, temperatures up to 1260°C are used and constant weight is possible even up to 2760°C (93). 

However, when the temperature is increased to 120°C, the principal reaction is the elimination to olefin. The thermal decomposition of dimethyl dodecyl amine oxide at 125°C in a sealed system, as opposed to a vacuum used by Cope and others, produces 2-methyl-5-decyhsoxa2ohdine, dimethyl dodecyl amine, and olefin (23). The amine oxide oxidi2es XW-diaLkylhydroxylainine to the nitrone during the pyrolysis and is reduced to a tertiary amine in the process. 

A2acyclobutenes have been used to generate l-a2abutadienes, which are intramolecularly as weU as intermolecularly cycli2ed to give tetrahydropyridines, eg, hexahydroquinoli2in-4-one [87842-80-6] (64,65). In the following, FVP = flash vacuum pyrolysis. 

The only commercially important dialkyl sulfates are dimethyl sulfate and diethyl sulfate. Estimated worldwide production in 1996 for dimethyl sulfate was 90,000 metric tons per year. Dimethyl sulfate was initially made by vacuum pyrolysis of methyl hydrogen sulfate ... 

Synthesis. Iminoboranes, thermodynamically unstable with respect to oligomerization can be isolated under laboratory conditions by making the oligomerization kineticaHy unfavorable. This is faciUtated by bulky substituents, high dilution, and low temperatures. The vacuum gas-phase pyrolysis of (trimethylsilylarnino)(aLkyl)haloboranes has been utilized as an effective method of generating iminoboranes RB=NR as shown in equation 19 for X = F,... 

By-product formation can also be reduced by use of a stripping gas or vacuum to faciUtate removal of ammonia (88) however, sublimation of urea becomes excessive if the pressure is too low. Addition of ammonium salts (eg, CU, NO7, or ) (89—91), acids, or pyrolysis of preformed urea salts, eg,... 

The majority of the cyanuric acid produced commercially is made via pyrolysis of urea [57-13-6] (mp 135°C) primarily employing either directiy or indirectly fired stainless steel rotary kilns. Small amounts of CA are produced by pyrolysis of urea in stirred batch or continuous reactors, over molten tin, or in sulfolane. The feed to the kilns can be either urea soHd, melt, or aqueous solution. Since conversion of urea to CA is endothermic and goes through a plastic stage, heat and mass transport are important process considerations. The kiln operates under slight vacuum. Air is drawn into the kiln to avoid explosive concentrations of ammonia (15—27 mol %). 

Flash vacuum pyrolysis of 2-methoxycarbonylpyrrole (11) gives the ketene (12), characterized by IR absorption at 2110 cm. On warming to -100 to -90 °C the dimer (13) is formed (82CC360). Flash vacuum pyrolysis of indole-2-carboxylic acid (14) results in loss of water and the formation of a ketene (15) showing absorption at 2106 cm (82CC360). 

The intermediacy of N-arylbenzotriazoles in the formation of carbazoles from o-anilinobenzenediazonium salts has already been mentioned in Section 3.03.2.3. The parallel conversion of 1,4- and 1,5-diphenyl-l,2,3-triazoles to 3-phenylindole with minor amounts of the 2-isomer has been effected by flash vacuum pyrolysis (Scheme 106a) (75JCS Pl)l). Similar treatment of 1,3,5- or 3,4,5-triphenyl-1,2,4-triazole provides 1,3-diphenylisoindole (Scheme 106b) <75JCS(P1)12>. 

Although formally it could be classified with the ring transformations (Section 4.04.3.2.2), conversion of 2,4-diphenyl-l,3,4-oxadiazol-2-one (593) by flash vacuum pyrolysis at 500 °C into 3-phenylindazole (595) involves a C(3)—C(3a) ring closure of the diphenylnitrilimine (594) (79AG(E)721). 

Acetonitrile oxide was generated from 3,4-dimethylfuroxan oxide by flash vacuum pyrolysis and trapped at -40 °C where its and NMR spectra were examined. Warming to room temperature in the presence of propane produced 3,5-dimethyl-2-isoxazoline (Scheme 108) (79TL2443). The oxide could also be generated by photolysis of furoxan (68CC977). 

The conversion of small rings to smaller ones, without loss, is not common. 3-Chloroazetidine isomerizes reversibly to 2-chloromethylaziridine (Section 5.09.2.2.5). Flash vacuum pyrolysis can convert isoxazoles to azirines (Section 5.04.4.3). More common is the isomerization of medium-sized, i.e. five- or six-membered rings, e.g. certain succinimides (Scheme 23) (81JOC27) to azetidinediones, or bicyclic 1,2-dioxetanes to bis-oxiranes (Section 5.05.4.3.2). 

The addition of phthalimidylnitrene (374) to simple alkynes affords 1-azirines in yields of 1-15% (Scheme 10). In this reaction, which is of no real preparative value, the symmetrical 2-azirines (375) were suggested as the most plausible intermediates and unequivocal proof of the existence of such species was demonstrated from a series of 1,2,3-triazole pyrolysis reactions <71CC1518). Extrusion of nitrogen from the regioisomeric 4,5-disubstituted 1,2,3-triazoles (376) during flash vacuum pyrolysis furnished identical product mixtures which included both regioisomeric 1-azirines (377). 

Although by no means a preparative route to either 1- or 2-azirines, the elimination of nitrogen (by flash vacuum pyrolysis at 400 °C) from the regioisomeric 4,5-disubstituted IH-1,2,3-triazoles (376) leads to similarly regioisomeric 1-azirines (377) <73JCS(P1)550). 

Pyrazolo[3,4-c]pyrazole, tetrahydro-rearrangement, 5, 250 Pyrazolo[4,3-c]pyrazole, tetraaryl-electrophilic substitution, 6, 1035 oxidation, 6, 1034-1035 reduction, 6, 1035 vacuum pyrolysis, 6, 1035 Pyrazolo[ 1,2-n]pyrazole-1,5-diones synthesis, 6, 991 Pyrazolo[ 1,2-n]pyrazoles reactions, 6, 1038 ring opening, 6, 983... 

High vacuum pyrolysis, heating in organic bases, contact with acidic adsorbents and reaction at room temperature with perchloric acid or boron trifluoride etherate cleaves the pyrazoline to give a 45-60% yield of the cyclopropane derivative (13) as well as 9 % of the unsaturated methyl compound (14). ° ... 

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