Propylene pyrolysis

Figure 3. Images of a cross-section of carbon fibers after propylene pyrolysis. 3a Scanning Electron Microscopy of a piece of the carbon cloth. 3b optical microscopy (crossed polarizers with a wave retarding plate).

Figure 3 c. HRTEM image of a cross-section of a carbon fiber after propylene pyrolysis the black line represents the boarder between the lamellar pyrocarbon (at the top) and the microporous fiber (at the bottom). 

A similar treatment of the propylene pyrolysis data at 750°C is shown in Figure 18. In this case, the calculated rates obtained by extrapolating Equation 2 to higher temperatures are much smaller than those determined by graphical differentiation of yield-to-residence time curves. The rate of formation of cyclics is linear with butadiene concentration. This... 

Figure 9. Ethylene and propylene pyrolysis (yield as per cent of feed converted)...

Verma, S. and P. Walker, Preparation of carbon molecular sieves by propylene pyrolysis over nickel-impregnated activated carbons. Carbon. 1993.31(7) p. 1203-1207. 

It was attempted in this study, therefore, to have a more detailed investigation of propylene pyrolysis in the presence of hydrogen. Furthermore propylene was subjected to pyrolysis in the presence of deuterium. Kinetic isotope effect was measured and deuterium distributions in the pyrolysis products were analyzed. 

Reactor Surface Effects During Propylene Pyrolysis... 

The thermal decomposition of propylene involves a series of primary and secondary reactions leading to a complex mixture of products. Studies showed that the distribution of pyrolysis products varies considerably with the pyrolysis conditions and the type of reactor used. There is agreement among the studies on propylene pyrolysis that the three major products of pyrolysis are methane, ethylene, and hydrogen. However, there is disagreement on the types and amounts of minor or secondary product species. Ethane, butenes, acetylene, methylacetylene, allene, and heavier aromatic components are reported in different studies, Laidler and Wojciechowski (1960), Kallend, et al. (1967), Amano and Uchiyama (1963), Sakakibara (1964), Sims, et al. (1971), Kunugi, et al. (1970), Mellouttee, et al. (1969), conducted at different conversion and temperature levels. Carbon was also reported as a product in the early work of Hurd and Eilers (1943) and in the more recent work of Sims, et al. (1971). 

The overall rate of propylene pyrolysis has been reported to be first order in some studies and as 3/2 order in others. Most studies conducted at low temperatures (up to 650C) tend to favor 3/2 order, while studies conducted at higher temperatures indicated mostly a first order rate. Clearly, the overall order of reaction is at best only a pseudo or an apparent order representing a combination of many elementary steps. 

KINETIC PARAMETERS OF PROPYLENE PYROLYSIS IN UNTREATED 304 STAINLESS STEEL REACTOR... 

Simple nth order kinetics are not adequate for representing propylene pyrolysis over any but a relatively short temperature and/or conversion range, A transition does occur from an overall propylene pyrolysis order of 1.5 to 1.0 as the temperature of reaction increases from 700 to 850C. 

Results indicate that the rate and amount of propylene cracking over the microporous activated carbon depends upon cracking conditions such as temperature, time and propylene partial pressure. Intense propylene pyrolysis conditions, such as high temperature and propylene concentration, favor carbon deposition. Thus, selection of proper experimental conditions is important for successful conversion of microporous carbons to useful molecular sieves. 

In all cases, CO2 uptake was higher than that of CH4. For samples prepared by CsHe cracking at 500°C, the uptake curves were quite similar, and equilibrium uptake capacity decreased at long cracking times. A significant reduction in uptake capacity was observed for samples prepared at 700°C, especially for CH4 and at long reaction periods. Selectivity ratios of samples prepared at 500 C varied between 2.9 and 4.1, while selectivities improved up to 10.4 for samples prepared at 700 C. The highest selectivity ratio was observed for CMS produced by propylene pyrolysis at 700°C for 60 min. 

Propylene Dimer. The synthesis of isoprene from propjiene (109,110) is a three-step process. The propjiene is dimeri2ed to 2-methyl-1-pentene, which is then isomeri2ed to 2-methyl-2-pentene in the vapor phase over siUca alumina catalyst. The last step is the pyrolysis of 2-methyi-2-pentene in a cracking furnace in the presence of (NH 2 (111,112). Isoprene is recovered from the resulting mixture by conventional distillation. 

Combination techniques such as microscopy—ftir and pyrolysis—ir have helped solve some particularly difficult separations and complex identifications. Microscopy—ftir has been used to determine the composition of copolymer fibers (22) polyacrylonitrile, methyl acrylate, and a dye-receptive organic sulfonate trimer have been identified in acryHc fiber. Both normal and grazing angle modes can be used to identify components (23). Pyrolysis—ir has been used to study polymer decomposition (24) and to determine the degree of cross-linking of sulfonated divinylbenzene—styrene copolymer (25) and ethylene or propylene levels and ratios in ethylene—propylene copolymers (26). 

Reversed-phase hplc has been used to separate PPG into its components using evaporative light scattering and uv detection of their 3,5-dinitroben2oyl derivatives. Acetonitrile—water or methanol—water mixtures effected the separation (175). Polymer glycols in PUR elastomers have been identified (176) by pyrolysis-gc. The pyrolysis was carried out at 600°C and produced a small amount of ethane, CO2, propane, and mostiy propylene, CO, and CH4. The species responsible for a musty odor present in some PUR foam was separated and identified by gc (Supelco SP-2100 capillary column)... 

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). 

Propjiene [115-07-17, CH2CH=CH2, is perhaps the oldest petrochemical feedstock and is one of the principal light olefins (1) (see Feedstocks). It is used widely as an alkylation (qv) or polymer—ga soline feedstock for octane improvement (see Gasoline and other motor fuels). In addition, large quantities of propylene are used ia plastics as polypropylene, and ia chemicals, eg, acrylonitrile (qv), propylene oxide (qv), 2-propanol, and cumene (qv) (see Olefin POLYMERS,polypropylene Propyl ALCOHOLS). Propylene is produced primarily as a by-product of petroleum (qv) refining and of ethylene (qv) production by steam pyrolysis. 

Significant products from a typical steam cracker are ethylene, propylene, butadiene, and pyrolysis gasoline. Typical wt % yields for butylenes from a steam cracker for different feedstocks are ethane, 0.3 propane, 1.2 50% ethane/50% propane mixture, 0.8 butane, 2.8 hill-range naphtha, 7.3 light gas oil, 4.3. A typical steam cracking plant cracks a mixture of feedstocks that results in butylenes yields of about 1% to 4%. These yields can be increased by almost 50% if cracking severity is lowered to maximize propylene production instead of ethylene. 

Superffex C t lytic Crocking. A new process called Superflex is being commercialized to produce predorninantiy propylene and butylenes from low valued hydrocarbon streams from an olefins complex (74). In this process, raffinates (from the aromatics recovery unit and the B—B stream after the recovery of isobutylene) and pyrolysis gasoline (after the removal of the C —Cg aromatics fraction) are catalyticaHy cracked to produce propylene, isobutylene, and a cmde C —Cg aromatics fraction. AH other by-products are recycled to extinction. 

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. 

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). 

Although ethylene is produced by various methods as follows, only a few are commercially proven thermal cracking of hydrocarbons, catalytic pyrolysis, membrane dehydrogenation of ethane, oxydehydrogenation of ethane, oxidative coupling of methane, methanol to ethylene, dehydration of ethanol, ethylene from coal, disproportionation of propylene, and ethylene as a by-product. 

After acid gas removal the pyrolysis gas from the last stage of compression is cooled by propylene refrigerant and sent to a condensate stripper. This tower separates the C and heavier products, which exit the bottom, from the and lighter components. 

Propane cracking is similar to ethane except for the furnace temperature, which is relatively lower (longer chain hydrocarbons crack easier). However, more by-products are formed than with ethane, and the separation section is more complex. Propane gives lower ethylene yield, higher propylene and butadiene yields, and significantly more aromatic pyrolysis gasoline. Residual gas (mainly H2 and methane) is about two and half times that produced when ethane is used. Increasing the severity... 

Viable operating eonditions were identified experimentally for maximising the produetion of ethylene, propylene, styrene and benzene from the pyrolysis of waste produets. Data are given for pyrolysis temperature, produet reaetion time, and quench time using a batch microreactor and a pilot-plant-sized reactor. 26 refs. CANADA... 

The use of pyrolysis for the recycling of mixed plastics is discussed and it is shown that fluidised bed pyrolysis is particularly advantageous. It is demonstrated that 25 to 45% of product gas with a high heating value and 30 to 50% of an oil rich in aromatics can be recovered. The oil is found to be comparable with that of a mixture of light benzene and bituminous coal tar. Up to 60% of ethylene and propylene can be produced by using mixed polyolefins as feedstock. It is suggested that, under appropriate conditions, the pyrolysis process could be successful commercially. 23 refs. 

Perfluoroallyl radical, C3F5, was obtained by vacuum pyrolysis (850-950°C, 10 Torr) of 1,5-perfluorohexadiene or of 3-iodopentafluoro-propylene (14) and was studied by pyrolytic mass spectrometry (Kagrama-nov et al., 1983b) and by IR spectroscopy in an argon matrix (Mal tsev et al., 1986). 

---