Pyrolysis, pressurized

P.R. Westmoreland, J.B. Howard, J.P. Long well, and A.M. Dean. Predictions of Rate Constants for Combustion and Pyrolysis Pressure and Temperature Effects Reactions by Bimolecular QRRK. AIChEJ., 32(12) 1971-1979,1986. 

It encompasses work published up to early 1990.150 different pyrolysis reactions are classified — a detailed discussion of each work is not intended. Instead — if reported in the original pubUcation — the temperature of pyrolysis, pressure, and yield of the reactions are listed in the reaction equations. For some interesting cases by-products that have been characterized are listed as well. By this treatment the scope of the sulfone pyrolysis becomes obvious. 

B.p. — 29X. Monomer used to form polymers (only under rather drastic conditions) or copolymers with C2F4 and vinylidene fluoride, CH2 = CF2. Hexafluoropropene may be prepared by thermal decomposition of CF3CF2CF2C02Na or is prepared commercially by low pressure pyrolysis of C2F4. 

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. 

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). 

The Beckstead-Derr-Price model (Fig. 1) considers both the gas-phase and condensed-phase reactions. It assumes heat release from the condensed phase, an oxidizer flame, a primary diffusion flame between the fuel and oxidizer decomposition products, and a final diffusion flame between the fuel decomposition products and the products of the oxidizer flame. Examination of the physical phenomena reveals an irregular surface on top of the unheated bulk of the propellant that consists of the binder undergoing pyrolysis, decomposing oxidizer particles, and an agglomeration of metallic particles. The oxidizer and fuel decomposition products mix and react exothermically in the three-dimensional zone above the surface for a distance that depends on the propellant composition, its microstmcture, and the ambient pressure and gas velocity. If aluminum is present, additional heat is subsequently produced at a comparatively large distance from the surface. Only small aluminum particles ignite and bum close enough to the surface to influence the propellant bum rate. The temperature of the surface is ca 500 to 1000°C compared to ca 300°C for double-base propellants. 

Pyrolysis of chlorodifluoromethane is a noncatalytic gas-phase reaction carried out in a flow reactor at atmospheric or sub atmospheric pressure yields can be as high as 95% at 590—900°C. The economics of monomer production is highly dependent on the yields of this process. A significant amount of hydrogen chloride waste product is generated during the formation of the carbon—fluorine bonds. 

In this pyrolysis, sub atmospheric partial pressures are achieved by employing a diluent such as steam. Because of the corrosive nature of the acids (HE and HCl) formed, the reactor design should include a platinum-lined tubular reactor made of nickel to allow atmospheric pressure reactions to be mn in the presence of a diluent. Because the pyrolysate contains numerous by-products that adversely affect polymerization, the TFE must be purified. Refinement of TFE is an extremely complex process, which contributes to the high cost of the monomer. Inhibitors are added to the purified monomer to avoid polymerization during storage terpenes such as t7-limonene and terpene B are effective (10). 

A report on the continuous flash pyrolysis of biomass at atmospheric pressure to produce Hquids iadicates that pyrolysis temperatures must be optimized to maximize Hquid yields (36). It has been found that a sharp maximum ia the Hquid yields vs temperature curves exist and that the yields drop off sharply on both sides of this maximum. Pure ceUulose has been found to have an optimum temperature for Hquids at 500°C, while the wheat straw and wood species tested have optimum temperatures at 600°C and 500°C, respectively. Organic Hquid yields were of the order of 65 wt % of the dry biomass fed, but contained relatively large quantities of organic acids. 

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. 

Coal pyrolysis has been studied at both reduced and elevated pressures (136), and in the presence of a variety of agents and atmospheres (137). Although important to the study of coal stmcture and reactions, coal pyrolysis, as a means to generate Hquids, has proved to have limited commercial value. 

Od condensed from the released volatdes from the second stage is filtered and catalyticady hydrotreated at high pressure to produce a synthetic cmde od. Medium heat-content gas produced after the removal of H2S and CO2 is suitable as clean fuel. The pyrolysis gas produced, however, is insufficient to provide the fuel requirement for the total plant. Residual char, 50—60% of the feed coal, has a heating value and sulfur content about the same as feed coal, and its utilisation may thus largely dictate process utdity. 

Thermal and Photochemical Reactions. Unsubstituted ethyleneimine has astonishing thermal stabihty. The reaction of ethyleneimine diluted with argon proceeds to give a mixture of unidentified compounds only at temperatures above 400°C (339). In a flow pyrolysis system under pressures of <1.33 kPa (<10 mm Hg) on quartz wool, isomerization to give /V-methylenemethylamine and ethylideneimine was observed only ia the temperature range 510—535°C. Higher temperatures result ia fragmentation (340). 

Commercially and industrially most important, ketene itself, H2C—C—O, is produced by pyrolysis of acetic acid [64-19-7]. In this process, high quahty acetic acid is evaporated and the vapor passed continuously through a radiant coil under reduced pressure at 740—760°C. 

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). 

Xylenes. The main appHcation of xylene isomers, primarily p- and 0-xylenes, is in the manufacture of plasticizers and polyester fibers and resins. Demands for xylene isomers and other aromatics such as benzene have steadily been increasing over the last two decades. The major source of xylenes is the catalytic reforming of naphtha and the pyrolysis of naphtha and gas oils. A significant amount of toluene and Cg aromatics, which have lower petrochemical value, is also produced by these processes. More valuable p- or 0-xylene isomers can be manufactured from these low value aromatics in a process complex consisting of transalkylation, eg, the Tatoray process and Mobil s toluene disproportionation (M lDP) and selective toluene disproportionation (MSTDP) processes isomerization, eg, the UOP Isomar process (88) and Mobil s high temperature isomerization (MHTI), low pressure isomerization (MLPI), and vapor-phase isomerization (MVPI) processes (89) and xylene isomer separation, eg, the UOP Parex process (90). 

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). 

Uses ndReactions. Some of the principal uses for P-pinene are for manufacturing terpene resins and for thermal isomerization (pyrolysis) to myrcene. The resins are made by Lewis acid (usuaUy AlCl ) polymerization of P-pinene, either as a homopolymer or as a copolymer with other terpenes such as limonene. P-Pinene polymerizes much easier than a-pinene and the resins are usehil in pressure-sensitive adhesives, hot-melt adhesives and coatings, and elastomeric sealants. One of the first syntheses of a new fragrance chemical from turpentine sources used formaldehyde with P-pinene in a Prins reaction to produce the alcohol, Nopol (26) (59). 

Myrcene Manufacture. An important commercial source for mycene is its manufacture by pyrolysis of p-piaene at 550—600°C (87). The thermal isomerization produces a mixture of about 75—77 wt % myrcene, 9% limonene, a small amount of T -limonene [499-97-8] and some decomposition products and dimers. The cmde mixture is usually used without purification for the production of the important alcohols nerol and geraniol. Myrcene may be purified by distillation but every precaution must be taken to prevent polymerization. The use of inhibitors and distillation at reduced pressures and moderate temperatures is recommended. Storage or shipment of myrcene in any purity should also include the addition of a polymerization inhibitor. 

Pyrolysis of CsjB Hg] at 230°C gives CS2IB2H2] (60%) along with some CS2IB2QH2Q], CS2IB22H22], and CsBH (93). The sensitivity of polyhedral expansion reactions to solvent, temperature, and pressure is further exemplified by the results ia dioxane at 120°C under pressure. To obtain the closo borane, NajB H J is first converted to Cs2[B2 H23], which can be pyrolyzed to give Cs2[B2 H2J (89). 

The Coastal process uses steam pyrolysis of isobutane to produce propylene and isobutylene (as weH as other cracked products). It has been suggested that the reaction be carried out at high pressure, >1480 kPa ( 15 atm), to facHitate product separation. This process was commercialized in the late 1960s at Coastal s Corpus Christi refinery. 

---