Propylene condensate

Figure 10-80. Exchanger ratings and specifications for propylene condenser.

Of interest is the relative composition of the LABs, particularly the different amount of 2-phenyl isomer and of nonlinear alkylates, given in Table 8. Branched alkylbenzene (BAB) formed by the AlCl3-catalyzed reaction between propylene, condensed to its tetramer, and benzene are less biodegradable and are termed biologically hard. LABs have to a large extent replaced BABs in the domestic markets because of their improved biodegradability. 

Because the gas sent to the membrane stage is cooled, the solubility of propylene in the membrane is enhanced, and the selectivity of the membrane unit is increased. The propylene condensate contains some dissolved nitrogen so the liquid is flashed at low pressure to remove this gas, producing a better than 99.5 % pure hydrocarbon product. A photograph of a propylene/nitrogen vent gas treatment system is shown in Figure 8.36. 

The feed gas is first compressed and then sent to a vapor condenser, operating at - 20°C. On cooling the gas, a portion of the vapor contained in the feed gas (in this case propylene), condenses and is removed as liquid. The condenser off-gas, containing uncondensed propylene, is sent to the membrane unit, which preferentially permeates the hydrocarbon vapor, leaving a 99% pure nitrogen residue stream. The propylene-enriched permeate gas is recycled to the incoming feed gas. The gas sent to the membrane unit comes directly from the chilled vapor condenser and is, therefore, saturated with propylene and cold. Under these conditions, the solubility of the hydrocarbon in the membrane is enhanced, and the membrane selectivity is high. 

The raw propylene condensate produced in the condenser contains some dissolved nitrogen, so the liquid is flashed at low pressure to remove this gas. The flash step offgas is recycled to the feed as shown in Figure 21.6. After flashing, the propylene product has a purity of better than 99.5%. The hybrid design takes advantage of the ability of condensation to produce a high-purity liquid and of membrane separation to... 

Allyl Bromide. Introduce into a 1-litre three-necked flask 250 g. (169 ml.) of 48 per cent, hydrobromic acid and then 75 g. (40-5 ml.) of concentrated sulphuric acid in portions, with shaking Anally add 58 g. (68 ml.) of pure allyl alcohol (Section 111,140). Fit the flask with a separatory funnel, a mechanical stirrer and an efficient condenser (preferably of the double surface type) set for downward distillation connect the flask to the condenser by a wide (6-8 mm.) bent tube. Place 75 g. (40 5 ml.) of concentrated sulphuric acid in the separatory funnel, set the stirrer in motion, and allow the acid to flow slowly into the warm solution. The allyl bromide will distil over (< 30 minutes). Wash the distillate with 5 per cent, sodium carbonate solution, followed by water, dry over anhydrous calcium chloride, and distil from a Claisen flask with a fractionating side arm or through a short column. The yield of allyl bromide, b.p. 69-72°, is 112 g. There is a small high-boiling fraction containing propylene dibromide. 

The Reaction. Acrolein has been produced commercially since 1938. The first commercial processes were based on the vapor-phase condensation of acetaldehyde and formaldehyde (1). In the 1940s a series of catalyst developments based on cuprous oxide and cupric selenites led to a vapor-phase propylene oxidation route to acrolein (7,8). In 1959 Shell was the first to commercialize this propylene oxidation to acrolein process. These early propylene oxidation catalysts were capable of only low per pass propylene conversions (ca 15%) and therefore required significant recycle of unreacted propylene (9—11). 

Liquid-phase condensation of formaldehyde with propylene, catalyzed by BF or H2SO4, gives butadiene (52,53). 

Polymerization in Hquid monomer was pioneered by RexaH Dmg and Chemical and Phillips Petroleum (United States). In the RexaH process, Hquid propylene is polymerized in a stirred reactor to form a polymer slurry. This suspension is transferred to a cyclone to separate the polymer from gaseous monomer under atmospheric pressure. The gaseous monomer is then compressed, condensed, and recycled to the polymerizer (123). In the Phillips process, polymerization occurs in loop reactors, increasing the ratio of available heat-transfer surface to reactor volume (124). In both of these processes, high catalyst residues necessitate post-reactor treatment of the polymer. 

Gas-phase polymerization of propylene was pioneered by BASF, who developed the Novolen process which uses stirred-bed reactors (Fig. 8) (125). Unreacted monomer is condensed and recycled to the polymerizer, providing additional removal of the heat of reaction. As in the early Hquid-phase systems, post-reactor treatment of the polymer is required to remove catalyst residues (126). The high content of atactic polymer in the final product limits its usefiilness in many markets. 

Uses. About 35% of the isophthahc acid is used to prepare unsaturated polyester resins. These are condensation products of isophthahc acid, an unsaturated dibasic acid, most likely maleic anhydride, and a glycol such as propylene glycol. The polymer is dissolved in an inhibited vinyl monomer, usually styrene with a quinone inhibitor. When this viscous hquid is treated with a catalyst, heat or free-radical initiation causes cross-linking and sohdification. A range of properties is possible depending on the reactants used and their ratios (97). 

Polyester resins can also be rapidly formed by the reaction of propylene oxide (5) with phthaUc and maleic anhydride. The reaction is initiated with a small fraction of glycol initiator containing a basic catalyst such as lithium carbonate. Molecular weight development is controlled by the concentration of initiator, and the highly exothermic reaction proceeds without the evolution of any condensate water. Although this technique provides many process benefits, the low extent of maleate isomerization achieved during the rapid formation of the polymer limits the reactivity and ultimate performance of these resins. 

Although the selectivity is high, minor amounts of by-products can form by dehydration, condensation, and oxidation, eg, propylene [115-07-17, diisopropyl ether, mesityl oxide [141-79-7] acetaldehyde [75-07-0], and propionaldehyde [123-38-6]. Hydrotalcites having different Al/(A1 + Mg) ratios have been used to describe a complete reaction network for dehydrogenation (17). This reaction can also be carried out in the Hquid phase. 

Catalysts. In industrial practice the composition of catalysts are usuaUy very complex. Tellurium is used in catalysts as a promoter or stmctural component (84). The catalysts are used to promote such diverse reactions as oxidation, ammoxidation, hydrogenation, dehydrogenation, halogenation, dehalogenation, and phenol condensation (85—87). Tellurium is added as a passivation promoter to nickel, iron, and vanadium catalysts. A cerium teUurium molybdate catalyst has successfliUy been used in a commercial operation for the ammoxidation of propylene to acrylonitrile (88). 

Historically, isobutyl alcohol was an unwanted by-product of the propylene Oxo reaction. Indeed, isobutyraldehyde the precursor of isobutyl alcohol was occasionally burned for fuel. However, more recentiy isobutyl alcohol has replaced -butyl alcohol in some appHcations where the branched alcohol appears to have preferred properties and stmcture. However, suppHes of isobutyl alcohol have declined relative to overall C-4 alcohols, especially in Europe, with the conversion of many Oxo plants to rhodium based processes which give higher normal to isobutyraldehyde isomer ratios. Further the supply of isobutyl alcohol at any given time can fluctuate greatly, since it is the lowest valued derivative of isobutyraldehyde, after neopentyl glycol, methyl isoamyl ketone and certain condensation products (10). 

The earhest commercial route to -butyraldehyde was a multistep process starting with ethanol, which was consecutively dehydrogenated to acetaldehyde, condensed to crotonaldehyde, and reduced to butyraldehyde. In the late 1960s, production of -butyraldehyde (and isobutyraldehyde) in Europe and the United States switched over largely to the Oxo reaction of propylene. 

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. 

The mbber is then separated from its solvent by steam stripping. The viscous cement is pumped into a violently agitated vessel partly full of boiling water. The hexane flashes off and, together with water vapor, passes overhead to a condenser and to a decanter for recovery and reuse after drying. Residual unpolymerized ethylene and propylene appear at the hexane condenser as noncondensibles, and are recovered for reuse after drying. The polymer, freed from its carrier solvent, falls into the water in the form of cmmb. 

Other Derivatives and Reactions. The vapor-phase condensation of ethanol to give acetone has been well documented in the Hterature (376—385) however, acetone is usually obtained as a by-product from the cumene (qv) process, by the direct oxidation of propylene, or from 2-propanol. 

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. 

Improved and redesigned rotors of modem compressors save considerable power. The ethylene fractionator and the propylene refrigeration condensers can be replaced with extended surface tube bundles instead of conventional tube bundles. 

Figure 8. Condenser duly for single-stage propylene refrigeration system.

The following information was used in olefin plant case studies to determine if the ethylene/propylene cascaded refrigeration systems had enough horsepower for various plant operations. The propylene was condensed against cooling water at 110°F and the ethylene was condensed against propylene at -20°F. For comparison, the horsepower requirements for each refrigerant alone are also shown. 

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