Styrene extraction

STEX [Styrene extraction] A process for extracting styrene from pyrolysis gasoline. Developed by Toray. 

Description Raw pyrolysis gasoline is prefractionated into a heartcut C8 stream. The resulting styrene concentrate is fed to an extractive-distillation column and mixed with a selective solvent, which extracts styrene to the tower bottoms. The rich solvent mixture is routed to a solvent-recovery column, which recycles lean solvent to the extractive-distillation column and recovers the styrene overhead. A final purification step produces a 99.9% styrene product containing less than 50 ppm phenyl acetylene. 

All the styrene monomer (bpi.oia - 145.2 C, s/J == 0.906. ) produced throughout the world is obtained directly or indiiectly from etbylbenzeoe. Most is product by dehydrogenation, while a certain amount is also obtained as a co-product of Ae manu- ctuie of propylene oxide. Some attempts have been made to extract styrene from liyrolysis C5- gasolines (Stex process by Toray, deserflied in Section 4.2J), but they have. not culminated in commercial plants. 

Sato, M., Extract styrene from pyrolysis gasoline . Hydrocarbon Processing, 52 (51 141-144 (1973). Morimoto, H., Tatsumi, M., Tbe Stex process. Extraction of styrene from pyrolysis gasoline Bull, of Japan FePtdeiim IRSL, 16 ( ) 38-42 (1974). 

STEX [Siyrene Extraction] A process for extracting styrene from pyrolysis gasoline. Developed by Toray. Chem. Eng. News, 27 Aug 2001,79(35), 28-30. 

PhenoHc-based resins have almost disappeared. A few other resin types are available commercially but have not made a significant impact. Inorganic materials retain importance in a number of areas where synthetic organic ion-exchange resins are not normally used. Only the latter are discussed here. This article places emphasis on the styrenic and acryHc resins that are made as small beads. Other forms of synthetic ion-exchange materials such as membranes, papers, fibers (qv), foams (qv), and Hquid extractants are not included (see Extraction, liquid-liquid Membrane technology Paper.). 

Benzene, toluene, and xylene are made mosdy from catalytic reforming of naphthas with units similar to those already discussed. As a gross mixture, these aromatics are the backbone of gasoline blending for high octane numbers. However, there are many chemicals derived from these same aromatics thus many aromatic petrochemicals have their beginning by selective extraction from naphtha or gas—oil reformate. Benzene and cyclohexane are responsible for products such as nylon and polyester fibers, polystyrene, epoxy resins (qv), phenolic resins (qv), and polyurethanes (see Fibers Styrene plastics Urethane POLYiffiRs). 

Commercial polystyrenes are normally rather pure polymers. The amount of styrene, ethylbenzene, styrene dimers and trimers, and other hydrocarbons is minimized by effective devolatilization or by the use of chemical initiators (33). Polystyrenes with low overall volatiles content have relatively high heat-deformation temperatures. The very low content of monomer and other solvents, eg, ethylbenzene, in PS is desirable in the packaging of food. The negligible level of extraction of organic materials from PS is of cmcial importance in this appHcation. 

Solvent Recovery. A mixture of methanol and methyl acetate is obtained after saponification. The methyl acetate can be sold as a solvent or converted back into acetic acid and methanol using a cationic-exchange resin such as a cross-linked styrene—sulfonic acid gel (273—276). The methyl acetate and methanol mixture is separated by extractive distillation using water or ethylene glycol (277—281). Water is preferred if the methyl acetate is to be hydroly2ed to acetic acid. The resulting acetic acid solution is concentrated by extraction or a2eotropic distillation. 

The other class of acrylic compatible tackifiers includes those based on ter-penes. Terpenes are monomers obtained by wood extraction or directly from pine tree sap. To make the polyterpene tackifiers, the monomers have to be polymerized under cationic conditions, typically with Lewis acid catalysis. To adjust properties such as solubility parameter and softening point, other materials such as styrene, phenol, limonene (derived from citrus peels), and others may be copolymerized with the terpenes. 

C. Aguilar, P. BottuII and R. M. Marce, On-line and off-line solid-phase extraction with styrene-divinylbenzene-membrane extr action disks for determining pesticides in... 

A solution of 21 g (0.15 mole) of perbenzoic acid (Chapter 17, Section II) in 250 ml of chloroform is prepared in a 500-ml round-bottom flask. Styrene (15 g, 0.145 mole) is added, and the solution is maintained at 0° for 24 hours with frequent shaking during the first hour. At the end of the reaction period, only the slight excess of perbenzoic acid remains. The benzoic acid is extracted from the reaction mixture by washing several times with 10% sodium hydroxide solution. The solution is then washed with water and dried over anhydrous sodium sulfate. Fractional distillation gives 24-26 g (69-75%) of 1,2-epoxyethylbenzene, bp 101 /40 mm. 

Figure 5.4-3 shows the results of a lifetime study for Wilke s catalyst dissolved, activated, and immobilized in the [EMIM][(CF3S02)2N]/compressed CO2 system. Over a period of more than 61 h, the active catalyst showed remarkably stable activity while the enantioselectivity dropped only slightly. These results clearly indicate - at least for the hydrovinylation of styrene with Wilke s catalyst - that an ionic liquid catalyst solution can show excellent catalytic performance in continuous product extraction with compressed CO2. 

Ethylbenzene (C6H5CH2CH3) is one of the Cg aromatic constituents in reformates and pyrolysis gasolines. It can be obtained by intensive fractionation of the aromatic extract, but only a small quantity of the demanded ethylbenzene is produced by this route. Most ethylbenzene is obtained by the alkylation of benzene with ethylene. Chapter 10 discusses conditions for producing ethylbenzene with benzene chemicals. The U.S. production of ethylbenzene was approximately 12.7 billion pounds in 1997. Essentially, all of it was directed for the production of styrene. 

Analytical procedures sensitive to 2 ppm for styrene and 0.05 ppm or less for other items were used for examining the extracts. Even under these exaggerated exposure conditions no detectable levels of the monomers, of the polymer, or of other potential residuals were observed. The materials are truly non-food-additive by the FDA definitions. Hydrogen cyanide was included in the list of substances for analysis since it can be present at low levels in commercial acrylonitrile monomer, and it has been reported as a thermal decomposition product of acrylonitrile polymers. As shown here, it is not detectable in extracts by tests sensitive to... 

These results, considered in relation to the direct addition tests of monomer and hydrogen cyanide in the previous table, demonstrate that there is no reason to expect styrene monomer extraction into soft drinks, even at levels well below those we can measure analytically. They also reinforce our hydrogen cyanide data. Further, they indicate that these beverages are not more extractive of Lopac containers than the normal simulating solvents. The tests confirm the chemical safety of the containers as beverage packages. 

However, other molecules exist which form free radicals of such high stability that they effectively stop the chain process. These molecules are called retarders or inhibitors the difference is one of degree, retarders merely slowing down the polymerisation reaction while inhibitors stop it completely. In practice vinyl monomers such as styrene and methyl methacrylate are stored with a trace of inhibitor in them to prevent any uncontrolled polymerisation before use. Prior to polymerisation these liquids must be freed from this inhibitor, often by aqueous extraction and/or distillation. 

Di Manro, A. et al.. Recovery of hesperidin from orange peel by concentration of extract son styrene-divinylbenzene resin, J. Agric. Food Chem., 47, 4391, 1999. 

Betzemeier et al. (1998) have used f-BuOOH, in the presence of a Pd(II) catalyst bearing perfluorinated ligands using a biphasic system of benzene and bromo perfluoro octane to convert a variety of olefins, such as styrene, p-substituted styrenes, vinyl naphthalene, 1-decene etc. to the corresponding ketone via a Wacker type process. Xia and Fell (1997) have used the Li salt of triphenylphosphine monosulphonic acid, which can be solubilized with methanol. A hydroformylation reaction is conducted and catalyst recovery is facilitated by removal of methanol when filtration or extraction with water can be practised. The aqueous solution can be evaporated and the solid salt can be dissolved in methanol and recycled. 

An SPE method has been developed to replace the classical LLP method. Water sample is extracted with an SPE column such as Cig and styrene-divinylbenzene copolymer (PS-2) cartridges, which consist of a reversed bonded-phase silica sorbent, provided as an extraction tool. This is a simple and rapid method, and applied to the determination of residual amounts of naproanilide, propanil, mefenacet, etc. This system determines the residual amounts of most of the pesticides and has been successfully applied to determination of pesticides in water. 

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