Ethylene/propylene production

Ethylene/propylene products reign supreme among the copolymers. They are elastomers. Plastics containing about 20% or more propylene perform like natural rubber and can be cured by peroxide cross-linking. They are faster to chemical and to ageing than other types of natural rubber. 

The petrochemical plant and refinery integration schemes offer lower cost routes to incremental ethylene/propylene production either via revamp modifications or in grassroots application [5,6],... 

Evidence for the equilibration of light olefins within SAPO-34 prior to diffusion out of the crystalline structure has been obtained by comparing the ethylene/propylene ratio in the MTO product with that calculated from thermodynamic equilibrium. Figure 12.7 shows the thermodynamic ratios of the C2-C5 olefins at 0 psig as a function of temperature. The concentration of ethylene increases at higher temperatures. The influence of equilibrium on the ethylene/propylene product ratio obtained with the MTO-100 catalyst over a range... 

Fig. 12.8 Relationship of Ethylene/Propylene product ratio over MTO-lOO catalyst with thermodynamic equilibrium...

Propylene. Unlike ethylene, propylene production does not represent the requirement for propylene derivatives. With few exceptions, propylene is not made on purpose but is obtained as a by-product of other processes. More specifically, large quantities of relatively low purity (40-70%) propylene are produced in refineries as a by-product of gasoline manufacture. Additionally, significant quantities of higher purity propylene originate in olefins plants, where ethylene is the primary product. However, only polymer-grade propylene (>99% pure) can in any way be considered an on-purpose product. To better understand... 

In the 1990s, natural rubber consumption exceeded 4 million metric tons while synthetic rubber consumption exceeded 7 million metric tons. Among synthetic rubbers the largest production was of SBR, polybutadiene, and ethylene-propylene. Production has been continually increasing in the 2000s. 

Today, more butadiene (BD) is produced from butene (another C4) through steam cracking of naphtha gas oil (a byproduct of ethylene/propylene production). Through extractive distillation of this C4 cracker stream, the butadiene is obtained. Com-... 

Today more butadiene is produced from butene (another C4) through steam cracking of naphtha gas oil from ethylene/propylene production (it is a byproduct of eth-ylene/propylene production). Through extractive distillation of this C4 cracker stream, the butadiene is obtained. Commonly the yield achieved forBD is dependent on the quality of the feedstocks used for ethylene production. Usually the heavier the feedstock, the greater the BD production. Reportedly, the lighU feedstock only yields about one-fifth the yield of butadiene compared to the heavy feedstock. 

Ethylene/Propylene Production Technologies, Chem Systems, Inc., Process Evaluation/Research Planning, 88-1 (July 1990). 

The influence of equilibrium on the ethylene/propylene product ratio obtained with SAPO-34 catalyst over a range of temperatures and pressures can be seen from (Fig. 35) [189]. The relationship is linear with a slope that is significantly greater than 1, indicating that ethylene is in excess of equilibrium on the small-pore zeolites. An explanation for this relationship is that ethylene and propylene are in equilibrium within the pore structure of the SAPO-34 molecular sieve. However, because the 0.43 nm pore diameter of the SAPO-34 is too small to allow propylene to take a straight-line path through the pore mouth, its diffusion is hindered relative to ethylene. This would imply that diffusion limitations are the key factor controlling the C " / C," ratio [189]. 

There are little or no olefins in crude oil or straight run (direct from crude distillation) products but they are found in refining products, particularly in the fractions coming from conversion of heavy fractions whether or not these processes are thermal or catalytic. The first few compounds of this family are very important raw materials for the petrochemical Industry e.g., ethylene, propylene, and butenes. 

Furthermore, treatment of the aminopalladation product with bromine affords aziridines[176]. The aziridine 160 was obtained stereoselectively from methylamine and 1-decene in 43% yield. The aminopalladation of PdCl2 complexes of ethylene, propylene, and 1-butene with diethylamine affords the unstable ir-alkylpalladium complex 161, which is converted into the stable chelated acylpalladium complex 162 by treatment with CO[177],... 

Acrylonitrile—Butadiene—Styrene. ABS is an important commercial polymer, with numerous apphcations. In the late 1950s, ABS was produced by emulsion grafting of styrene-acrylonitrile copolymers onto polybutadiene latex particles. This method continues to be the basis for a considerable volume of ABS manufacture. More recently, ABS has also been produced by continuous mass and mass-suspension processes (237). The various products may be mechanically blended for optimizing properties and cost. Brittle SAN, toughened by SAN-grafted ethylene—propylene and acrylate mbbets, is used in outdoor apphcations. Flame retardancy of ABS is improved by chlorinated PE and other flame-retarding additives (237). 

Most of the industrially important alkyl aromatics used for petrochemical intermediates are produced by alkylating benzene [71-43-2] with monoolefins. The most important monoolefins for the production of ethylbenzene, cumene, and detergent alkylate are ethylene, propylene, and olefins with 10—18 carbons, respectively. This section focuses primarily on these alkylation technologies. 

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. 

Production estimates for propylene can only be approximated. Refinery propylene may be diverted captively to fuel or gasoline uses whenever recovery is uneconomic. Steam-cracker propylene production varies with feedstock and operating conditions. Moreover, because propylene is a by-product, production rates depend on gasoline and ethylene demand. 

ELASTOPffiRS,SYNTHETic-POLYcm.OROPRENE Elastop rs, SYNTHETIC-ETHYLENE-PROPYLENE-DIENE RUBBER). Tires, hoses, belts, molded and extmded goods, and asphalt products consume ca 80% of the reclaimed mbber manufactured. Typical properties of reclaimed mbbers are shown in Table 5. 

Ethylene—Propylene Rubber. Ethylene and propjiene copolymerize to produce a wide range of elastomeric and thermoplastic products. Often a third monomer such dicyclopentadiene, hexadiene, or ethylene norbomene is incorporated at 2—12% into the polymer backbone and leads to the designation ethylene—propylene—diene monomer (EPDM) mbber (see Elastomers, synthetic-ethylene-propylene-diene rubber). The third monomer introduces sites of unsaturation that allow vulcanization by conventional sulfur cures. At high levels of third monomer it is possible to achieve cure rates that are equivalent to conventional mbbers such as SBR and PBD. Ethylene—propylene mbber (EPR) requires peroxide vulcanization. 

Reaction and Heat-Transfer Solvents. Many industrial production processes use solvents as reaction media. Ethylene and propylene are polymerized in hydrocarbon solvents, which dissolves the gaseous reactant and also removes the heat of reaction. Because the polymer is not soluble in the hydrocarbon solvent, polymer recovery is a simple physical operation. Ethylene oxide production is exothermic and the catalyst-filled reaction tubes are surrounded by hydrocarbon heat-transfer duid. 

Short-chain alkylated biphenyls are the principal biphenyl derivatives in commercial use. They are generally produced by Hquid-phase Friedel-Crafts alkylation of biphenyl with ethylene, propylene, or mixed butenes. A series of mixed ethylated biphenyl heat-transfer fluids (trademarked Therm S-600, 700, 800) is marketed by Nippon Steel. A mixed diethylbenzene—ethylbiphenyl heat-transfer fluid is also available from Dow (63). Monoisopropylbiphenyl [25640-78-2] largely as a mixture of meta- and para-isomers is produced by Koch Chemical Co. Monoisopropylbiphenyl (MIPB) was selected by Westinghouse (64,65) as a PCB replacement in capacitors and this is its primary appHcation today. For a time MIPB was also employed as a PCB replacement in pressure sensitive copy paper, but this outlet has since given way to other dye solvents. A similar product consisting of a mixture of j -butylbiphenyl isomers [38784-93-9] (66) is currently the favored dye solvent for pressure sensitive copy paper (67) manufactured in the United States. 

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. 

The economic importance of copolymers can be cleady illustrated by a comparison of U.S. production of various homopolymer and copolymer elastomers and resins (102). Figure 5 shows the relative contribution of elastomeric copolymers (SBR, ethylene—propylene, nitrile mbber) and elastomeric homopolymers (polybutadiene, polyisoprene) to the total production of synthetic elastomers. Clearly, SBR, a random copolymer, constitutes the bulk of the entire U.S. production. Copolymers of ethylene and propylene, and nitrile mbber (a random copolymer of butadiene and acrylonitrile) are manufactured in smaller quantities. Nevertheless, the latter copolymers approach the volume of elastomeric butadiene homopolymers. 

The dephlegmator process recovers a substantially higher purity C2+ hydrocarbon product with 50—75% lower methane content than the conventional partial condensation process. The C2+ product from the cryogenic separation process can be compressed and further separated in a de-ethanizer column to provide a high purity C3+ (LPG) product and a mixed ethylene—ethane product with 10—15% methane. Additional refrigeration for the deethanization process can be provided by a package Freon, propane or propylene refrigeration system. 

Although the mbbery properties of ethylene—propylene copolymers are exhibited over a broad range of compositions, weight percentages of commercial products generally range from 50 50 to 75 25 ethylene propylene. 

The propylene fractionator operates at a pressure of 1.8 to 2.0 MPa with more than 160 trays required for a high purity propylene product. Often a two-tower design is employed when polymer grade (99.5%+) is required. A pasteurization section may also be used when high purity is required. The bottoms product contains mainly propane that can be recycled to the cracking heaters or used as fuel. Typical tower dimensions and internals for a 450,000 t/yr ethylene plant with naphtha feed are summarized in Table 7. 

Polytetrafluoroethylene and fluorinated ethylene-propylene are the only resins composed wholly of fluorine and carbon. The polymer consists of fluorine atoms surrounding the carbon chain as a sheath, giving a chemically inert and relatively dense product from the strong carbon-fluorine bonds. Polytetrafluoroethylene must be molded at high pressure. Fluorinated ethylene-propylene c.m be injection molded and extruded as thin fdm. Both plastics have exceptional heat resistance... 

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