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    • 专利摘要:
    1418974 Methyl substituted acetophenone SUMITOMO CHEMICAL CO Ltd 23 May 1973 [26 May 1972] 24752/73 Heading C2C [Also in Division C5] A mixture of o- and p-methylacetophenone is obtained by adding acetylchloride to an aluminium bromide/hydrogen bromide/toluene complex at 25-30‹ C., maintaining the mixture at 70‹ C. for 1 hour, treating with dilute, hydrochloric acid, water and then with caustic soda, and removing toluene by distillation. The complex used is prepared by continuously passing hydrogen bromide into the lower part of a bed of aluminium chips in contact with toluene and removing the resulting complex from the bottom of the bed.
    公开号:SU953985A3
    申请号:SU731934652
    申请日:1973-05-25
    公开日:1982-08-23
    发明作者:Еситаке Хироси；Танимото Кендзи；Котера Норио
    申请人:Сумитомо Кемикал Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    (54) FOCUS ON GETTING ALUMINUM TO A GALOID COMPLEX
    one
    The present invention relates to the production of aluminum halide cochlexes used as an alkylation and isomerization catalyst.
    Anhydrous aluminum halide compounds are known, in particular anhydrous chlorinated aluminum, which are used as catalysts for alkylation, transalkylation, isomerization, and expansion reactions 1.
    However, these catalysts are usually used in the form of pieces or granules, or powders, which make them difficult to use in production, because aluminum chloride powder hardens on the reactor pipe or on the way to this pipe, clogging it and disrupting the normal operation of the reactor.
    Closest to the invention, technical solu- tion is a method for producing an agamenium-halide KCHvomeKa, which is used as an alkylation catalyst and isomerization catalyst, by contacting aluminum, hydrogen halide and alkylbenzene. The known method consists in passing a hydrogen halide gas, such as hydrogen chloride, hydrogen bromide or hydrogen iodide, through a layer of aluminum cups from 0, 1 to 1.0 mm in size, immersed in anisole or oxygen and from the zone of contact 2.
    The disadvantage of this method is that the yield of the desired product is not sufficiently high, which is associated with the side reaction of the benzene alkylbenzene core hydrogenation.
    The purpose of the invention is to increase the yield of the target product - the aluminum-halide complex.
    This goal is achieved in that the preparation of an alumina-halide complex used as an alkylation and isomerization catalyst 20 is carried out by contacting aluminum, hydrogen halide and alkylhexol, while hydrogen gas is continuously fed into the lower part of the reaction zone containing aluminum and alkypbenzop and inductures and the synthesizer. the resulting alkali-halide complex is removed from the lower part of the reaction zone and the reaction byproduct is formed — hydrogen gas is removed from the upper part of the reaction Hshonnoy yony, maintain the temperature in the reaction zone from 40 to 20 ° C using aluminum in the form of pieces with a diameter of from 3 to 1 mm and uninterrupted or periodical supply of aluminum and alkkbenzopa in the reaction zone. The aluminum used in the proposed method does not need to be of high purity. In QUALITY ve alkylbenzenes most suitable toluene epotbenzol, dietipbenzol, trietylbenzol, etiltolusm, diethyl toluene, xylenes, trimetilbenvopy, etilksiloly, isopropylbenzene, dshzopropipbenzoly, triisopropylbenzene, izopropyLToluoly, dkizoprsgoshtoluoly, izopropilkstshgoly, izopropilettshbenzoly, secondary butyl benzene, di-secondary butyl benzene, vtortganye butiltoluopy, di - secondary butyltoluops, secondary butepspillols, secondary bupshethylbenzenes, hexylbenzoes, shlohexylbenzenes, and mixtures thereof. Hydrogen halides use moisture content in them to a total of less than 0.1%. They can contain free hydrogen, and also halogens to some extent: Preferred are hydrogen chloride and hydrogen bromide. The scaling rate of the hydrogen halide feed to the reaction zone is from 1 to 500 mm / s with separation of the gas in a conventional column. The molar ratio of hydrogen halide to aluminum fed is between 1/100 and 10 mol / h. The reaction temperatures vary according to the type of alkyl benzenes and hydrogen halide compounds and the relative surface area of the aluminum layer; the process temperature is maintained in the range of 20-2 ° C. Too low temperatures reduce the reaction rate, and too high temperatures cause the formation of by-products and the deterioration of catalytic activity: 1H of the resulting complexes. The oqeijb reaction carried out is exothermic and the heat of reaction can be removed from the reaction device either by evaporating the alkyl benzenes or by cooling the reaction zone. Example. A glass reaction column with a diameter of 70 mm is filled with 540 g of aluminum in the form of thin slices, each having a width of 1. 15 to 25 M and 2000 g of toluene is added thereto. Dried hydrogen chloride is blown through the aluminum layer on the bottom side at a rate of about 250 g / h. The reaction proceeds at 105-107s with a tart current. The resulting aluminum-chlorine kyosheks taken from the bottom and accumulate in the drive. After 4 hours of reaction, 123 g of aluminum was consumed and 3670 g of brown aluminum-chloride complex was obtained. The complex contains 26% aluminum chloride and 3% hydrogen chloride, the rest is organic components. The complex is stored in a closed vessel. PRI mme R 2. A glass reaction column with a diameter of 40 mm and a length of 700 mm g with a water jacket is filled with aluminum pieces with a diameter and a thickness of 10 mm and 3 mm, respectively, to a level of 500 mm from the bottom, and then filled with a mixture of 10 weight. % benzene and 90 wt. % secondary butyl benzene. After heating the column to 90 ° C, dried hydrogen chloride gas is passed through it at a rate of 22.4 n. l per hour, and then the column is cooled by passing cold water through a cooling jacket. When the reaction proceeds at 90 ° C for 4 hours, the average rate of complex formation is 113 g per hour, and the average consumption rate of aluminum is 7.25 g / h. There was no hydrogen chloride in the exhaust gas. The resulting complex is effective as a catalyst for the production of mono- and di-secondary butylbenzene from benzene and n-butene. Example 3. A nozzle made in the form of Raschig rings with a diameter of 7 mm (material — porcelain) is placed in the synthesis reactor of the complex and spaced 20 cm from the perforated plate on which aluminum droplets with a diameter of 2.5 cm are placed (purity 99.7 aluminum). %). Aluminum is laid to a height of 67 cm above the previous layer. Toluene is fed up to the level of 1OO cm above the plate, and air, with a capacitance of 15 kg) and yes, with a nitrogen gas, followed by hydrogen chloride — at a rate of 2.4 cm / s. The countercurrent of toluene is carried out at 110-113. The resulting aluminum-chloride compound and the complex gives rise to a storage ring and is collected under a layer of toluene. The aluminum-chloride complex is removed from the floor and the toluene is fed to maintain the upper surface at a certain level. After 24 h, the reactivity of the aluminum layer is reduced to 23 cm. After that, the supply of hydrogen chloride is stopped and the aluminum granules are added in such a quantity as to restore the original height of 67 cm. The amount of regenerated hydrogen chloride i (absorbed in basal hydrochloric acid) is about 9% by weight of the amount of hydrogen chloride fed to the reactor. The hydrogen released during the process is hydrogen gas that is washed with an alkali solution and used as fuel. The complex of aluminum chloride obtained in this way weighs approximately 19 times the amount of consumed aluminum. The complex is used in the preparation of isopropyltoluene from toluene and propylene, as well as in the preparation of isoproshtoluene from toluene to diisopropyltoluopene. Example 4. In Example 1, hydrogen chloride is replaced by hydrogen bromide, the consumption of which is 555 g / hr. To 656 g of the complex thus obtained (267 g is aluminum bromide) 80 g of acetyl chloride are added at 25-30 ° C and then the temperature increase to 70 ° C and maintain for 1 hour. After this, the solution is treated with dilute hydrochloric acid, then with water, and then with a solution of caustic soda. Toluene is distilled off. EXAMPLE 5 Example 1 is repeated. Except that a mixture of 5% benzene and 95% cumene is used instead of toluene, hydrogen chloride sparks at 85 ° C and the reaction lasts 2 hours, resulting in about 18OO g of complex containing 2O% aluminum chloride and 4% hydrogen chloride. A mixture of 43.4 g of benzene and 148 triisopropylbenzene is reacted at 100 ° C for 1 h in the presence of 2.7 g (0.8 g of aluminum chloride) of the resulting complex, c. the result of which is a mixture that gives 2.5%. 25.0% kumopa, 58% P-diisopropylbenzene, and 14% 1,3,5-triyzosch szhilbenzol. EXAMPLE 6 (By a known method) 30 g of powdered aluminum H 1 l of toluene is loaded into a two-liter four-wheeled bottle equipped. with a stirrer, a gas injection tube, a soldering station and a thermometer, and gaseous hydrogen chloride is bubbled into the mixture at a rate of 1OO g / h per hour at HO C for 3 hours at a boiling point with reverse chardash. This gives 56O g of a reddish brown complex aluminum chloride compound containing 0.45 g of unreacted aluminum, 26% aluminum chloride and 3% hydrogen chloride. The rest is accounted for by the organic components containing 5, 6% of the compounds hydrogenated in the core. EXAMPLE 7 (By a known method) Example 6 is repeated using, instead of toluene, pseudocumene (1,2,4-trimethylbenzene) with the reaction temperature controlled in the range of 105. In this case, OO5O5 g of a reddish-dark-brown complex compound of aluminum chloride, -Soder-, of 0.4 g of unreacted alumina, 29% of aluminum chloride and 4% of hydrogen chloride is obtained. The remainder is accounted for by the organic components, containing 6.1% of the compound grated in the core. PRI me R 8. (Comparative). A 1OOO-ml flask equipped with a stirrer, a gas inlet tube, inlets for feeding toluene and a gas tank and toluene and a shedon tube are fed 133 g / h of toluene, 27 g / h of diisopropyltoluene, 35 g / h of propylene and 6.0 g / h h complex of aluminum chloride, obtained in example 1 and 7, with the regulation of the reaction temperature at the level of 1OO in a water bath (time and cheeks 4 hours). The contents of the obtained products are given in the table. Example E. 1,2,3,5-tetramethylbenzene instead of toluene is charged to the glass reaction column of Example 1 with the same amount of aluminum filler, with the same purging parameters with hydrogen chloride. The reaction system reaches a boiling point approximately 70 minutes after purging with dry gas, hydrogen chloride, and the reaction is continued at 195-2OOC in reflux mode. After 4 hours of reaction, 215 g of alu was consumed. P 1: O g chenoZ, 51O g of an Alkaline chloride complex of brownish color. The complex thus obtained contains 30.3% aluminum chloride and 3.5% hydrogen chloride, and the rest up to 1OO% consists of organic components. 1 g of the obtained complex is added to 1OO g of srt-xylene and the mixture is maintained at 130 ° C for 2 hours, resulting in
    pezuyuchkgg o Les, with an erecapi of 63% metaxpopa and 18.5% para-xc pop.
    Example 10. Glass reaction spoil with a diameter of 4 mm and a length of 700 mm, heating and cooling of which is produced by means of a water jacket, is filled with tablets of aluminum with a purity of 99.7%, which is 5 mm in diameter and 3 mm thick, to a level of 50 mm from the bottom of the column, and then the column is filled with toluene. A sump is directly attached to the bottom of the reaction column, which is filled with toluens l.
    The reaction column is heated to 40c and dry hydrogen chloride is passed through it at a flow rate of 50 g / h, after which the column is immediately contaminated.
    by passing water through the jacket, so that the internal temperature of the reaction column is kept at about the same level. Not much reflux is found in the refrigerator. The reaction proceeds at 40 ° C for 4 hours. As a result, 44 g of aluminum are consumed; 837 g of slightly yellow-brown aluminum-chloride complex are obtained. The thus obtained Xpopex contains 26% chloride) aluminum and 3% hydrogen chloride, and the rest up to 1OO% consists of organic components. Organic components contain about 0.1% of compounds hydrogenated in the core. The resulting alumina complex is used in the reaction according to Example 9n and the same results are obtained.
    权利要求:
    Claims (1)
    [1]
    Claim
    A method of producing an aluminum halide complex used as an alkylation and isomerization catalyst by contacting aluminum, halobenzoic acid and alkylbenzene, characterized in that, with a chain to increase the yield of the target product, gaseous hydrogen halide is continuously fed to the lower part of the reaction zone containing aluminum and alkylbeneop, and the resulting aluminum halide complex is continuously removed from the lower part of the reaction zone, and the resulting by-product of the reaction, gaseous hydrogen, is removed from the upper parts of the reaction zone, while maintaining the temperature in the reaction zone from. 40 to 200 d C, use aluminum in the form of pieces with a diameter of 3 to 100 mm and carry out continuous or periodic supply of aluminum and alkylbenzene to the reaction aeon.
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    同族专利:
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    FR2189354B1|1976-11-12|
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    引用文献:
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    DE1101420B|1958-11-28|1961-03-09|Hoechst Ag|Process for the production of catalytically active, anhydrous aluminum chloride suspensions for organic-chemical reactions|
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    JP2797486B2|1989-07-25|1998-09-17|住友化学工業株式会社|Method for producing 2-alkylresorcinol|
    US5104846A|1989-08-23|1992-04-14|Viswanatha Sankaran|Molecular restructuring catalyst|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP47052759A|JPS497230A|1972-05-26|1972-05-26|
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