• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A catalytic process is provided for the ethylation of a mono alkyl benzene wherein the alkyl group contains 1 or 2 carbon atoms, i.e. toluene or ethylbenzene to yield a mixture of ethyl toluene or diethylbenzene isomers with minimal undesired by-product formation which comprises contacting said mono alkyl benzene under conversion conditions, with an ethylating agent in the presence of a catalyst comprising a crystalline aluminosilicate zeolite characterized by a constraint index, as hereinafter defined, within the approximate range of 1 to 12 and a silica to alumina ratio greater than about 500.
    公开号:SU1181532A3
    申请号:SU782627506
    申请日:1978-06-22
    公开日:1985-09-23
    发明作者:Вильям Каединг Уоррен
    申请人:Мобил Ойл Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    cl
    C 1 The invention relates to spores of preparing mixtures of isomers of ethyltoluene or diethylbenzene by catalytic ethylation of toluene or ethylbenzene. Ethyltoluene and diethylbenzene are used as a raw material in the preparation of vinyltoluene and divinylbenzene by dehydrogenation. Therefore, it is important to obtain isomers of ethyltoluene and distilbenzene with a minimum content of undesirable by-products, especially aromatic products that are difficult to separate from the target products using expensive operations. cleaning up. The aim of the invention is to increase the selectivity of the process by reducing the formation of aromatic byproducts and light gassing: 1st by-products. Example 1. Zeolite ZSM-5, characterized by a high silica / aluminum molar ratio, is prepared as follows. Pre-cooking. 16.524 g of methyl ketone; 10.008 g of three-n-proshamine and 8604 g of n-propplbromide are loaded into a 114 l autoclave, the components are mixed with gentle stirring for 15 minutes. The stirring is stopped and 55842 waters are loaded into the autoclave. The autoclave is sealed and heated to 104 Cj and held at 104 ° C for 15 hours. After the reaction, the temperature is raised to 160c and the unreacted organic matter is melted. An aqueous layer containing pre-reacted organics and 1, 44 wt. nitrogen is removed. Synthesis of zeolite. Preparation of silicate solution: 41269 g of sodium silicate, 23880 g of H, 0, 118 g of Daxad 27 (sodium salt is a polymerized substituted benzene alkyl-sulfonic acid combined with the suspended agent). Preparation of an acidic solution: 4138 g of H5, S04, 1840 g of NaCI, 50.7 g of pre-reacted organics, 6674 g, additional solid substances, 5890 g of Nad, additional liquid, 1180 g of HgO. The silicate solution and the acidic solution are mixed in a mixer with the formation of a gel, which is fed to an autoclave 5322 with a capacity of 144 liters, which also serves 1180 g of Water. The gel is stirred and 5890 g of NaCl is added and the components are completely mixed. The autoclave is closed and heated to 104c with stirring at a speed of 90 rpm and held for 54.3 hours until crystallization is complete. The contents of the autoclave are cooled and discharged. The crystallization product is analyzed by X-ray diffraction. It contains 100 May. % ZSM-5. The chemical analysis of the completely washed crystalline product is presented in Table. 1. Table 1 Example 2. ZSM-5, having a molar ratio of silicon to aluminum of about 70, is prepared in the following manner. 830796 g of tri-n-propylamine is mixed with 730940 g of n-propyl bromide, 1407400 g of methyl lithium ketone and 4746 l of deionized water. The mixture was subjected to reaction at 99-103 C, stirred at a speed of 5 rpm for 14 hours in an autoclave equipped with a high-power mixer. The resulting aqueous phase is referred to as solution A. 2218 L of deionized Veda is mixed with the required amount of sodium silicate to give a solution with a specific gravity of 1.222. 10896 g of Daxad 27 are added to the solution. The resulting solution is referred to as solution B. 138470 g of apoy- technical sulfate; Min (17.2Z) is dissolved in 1654 L of deionized water. To this 3 solution, 332782 g of sulfuric acid (93.2 wt.% H2SO4), 171158 g of technical NaCl and 869410 g of solution A are added. The resulting solution is designated solution C, 76 l of deionized water are added to a high pressure autoclave. effective stirrer. Solution B and solution C are mixed in a vessel and placed in an autoclave. 544800 g of technical NaCl is added to the autoclave. The resulting gel is stirred in an autoclave at a speed of 90 rpm and at room temperature for 4 hours. The gel is then reacted at 97-108 ° C and a stirring speed of 90 rpm for 40 hours and at 160 ° C and at 90 rpm for 3 hours. The solid product is analyzed by X-ray diffraction and thus ZSM-5 is identified. The solid is washed by decantation with deionized water and 3500 ppm of Primaflok C-7 (polyammonium bisulfate) until the sodium content is. the product will not be less than 1%. Solid product is filtered on a rotary drum filter. The resulting briquette dried as a result of filtration occurs at 154 C. The chemical composition of the dry product is presented in Table. 2. Faces Prod Lesser tlG ..--. 3 1362-1816 g of the dry product is calcined in Nj for 3 hours at 538 C. 1329 g of the calcined product are mixed with 6645 cm of 1N solution for 1 hour at room temperature. The mixture is subjected to filtration under vacuum. The ion exchange procedure is repeated and the briquette remaining on the filter is extruded at 121 ° C. The sodium content in the final product is less than 0.5% by weight. Examples 3-6. Toluene is alkylated with ethylene using the catalysts obtained in Example 1 and 2. The process is carried out at atmospheric pressure for about 20 hours. The catalyst is diluted with three volumes of quartz fragments with a low surface area. Samples are taken for analysis during the first and last hours of each stage, in order to obtain the tabulated data. The reaction conditions and the results are shown in Table. 3
    From the above comparative data, it is clear that using a ZSM-5 catalyst with a high ratio of i is typical of the catalyst of Example 1, and a significant reduction in the formation of undesirable by-products is realized. A comparison of the selectivity to the reaction of formation of by-products is presented in Table. four.
    Table u
    From tab. 4, it can be seen that at the reaction temperature the catalysts lead to a decrease in undesirable by-products, by about 3-7 times. and you can use zeolite. catalyst at a high SiO / AljO H ratio at 400 ° C. Significantly Bbmje reduction of side products of the reaction, approximately 11-21 times A. Example catalyst (SiO / AljO, 1670/1) 7.215.5-5.6 27-tO 36 , 9-51.1 86.1-82.0 0.55. B. Catalyst of Example .2 (SiOj / AljOj 68.9) 7,153.3-54.2 68-65 28.9-29.2 53.8-52.7 0.47. 20.3-4.5 86-3.4 35.5-51.1 77.5-71.9 4.6-2.7 The range shows the results for the first and next time period and,
    From tab. 5 that the selectivity to the desired diethylbenzene product is significantly Bbmie when using a catalyst with a higher Si02 / Alj ratio, 0 (1670/1), and the formation of by-product gases and other aromatic compounds, respectively, is lower.
    A catalyst with a lower SiO / AljOg ratio (68.9 / 1) is significantly more active, as indicated by a high conversion of ethylbenzene. fe in the case of formation of light gases and approximately 45-83 times, in the case of the formation of aromatic hydrocarbons. Examples 7-9. Similar to Examples 3-6, using the catalysts described in Examples 1 and 2, isoplification of ethylbenzene with ethylene is carried out. Reaction conditions and analysis results are presented in Table. 5. Table IS 0.4-0.8 13.5-17.2 5.8-6.1 40.4-41.2 17.9-25.4 hours of reaction ha specified
    9118153210
    at 350 ° C. Even when the temperature is as follows. The process is conducted
    is lowered to 250 ° C in order to reduce con-analogy to examples 3-6, but with the use of, a relatively large amount of ZSM-5 with the ratio
    byproducts are obtained by SiOj / AljOg 500, temperature
    compared with products obtained with j and pressure of 1 atm; using a catalyst with a higher SiOj / AljOj ratio. The results are given in. 6. Indicators Results WHSV toluene 7.38 6.50 6.79 WHSV ethylene 0.47 0.47 0.47 Molar ratio toluene-4.80 4.22 4.41 Conversion, wt.% Toluene 17.8 19 , 6 19.5 89.4 86.3 85.0 84.1 ethylene Selectivity by product, May. % p-ethyltoluene 31.99 32.97 31.98 M-ETSh1TOLUOL-62.85 65.6463.12 0-ETYLT5LUOL 3.71 -3.62 light gases 0.23 0.200.20 other aromatics 1.22 1.191, 09
    That 5, 6 process using a catalyst according to example 10 6.86 6.86 6.78 6.67 0.47 0.47 0.47 0.47 4.45 4.45 4.40 4.33 18.6 18 , 4 18,8 18,7 83,5 87,5 81,2 32,12 32,18 32,76 33,50 53,15 63,1563,1162,86 3,493., 63,072,63 0,170,160,120,15 1,061,040,940, 87
    权利要求:
    Claims (1)
    [1]
    - METHOD FOR PRODUCING MIXTURES
    Ethyltoluene or diethylbenzene isomers by ethylation of toluene or ethylbenzene with ethylene in the presence of an o -zeolite catalyst of type ZSM-5 at 350-400 C, atmospheric pressure, mass feed rate of toluene or ethylbenzene 3.5-7.4 per unit mass of catalyst in hour and a molar ratio of toluene or ethylbenzene to ethylene of 3.4-4.8, characterized in that, in order to increase the selectivity of the process, use zeolite ZSM-5 with a molar ratio of SiO a and A1 2 0z equal to 500-1670.
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    同族专利:
    公开号 | 公开日
    DE2826865A1|1979-01-18|
    CA1110278A|1981-10-06|
    BE868116A|1978-12-14|
    PL207835A1|1979-05-21|
    IT1096780B|1985-08-26|
    FR2395242B1|1983-12-09|
    US4104319A|1978-08-01|
    DD137705A5|1979-09-19|
    RO81507B|1983-04-30|
    NL7806750A|1978-12-28|
    ES471028A1|1979-09-16|
    PL111568B1|1980-09-30|
    AU3733278A|1980-01-03|
    RO81507A|1983-04-29|
    GB1587298A|1981-04-01|
    ZA783457B|1980-02-27|
    FR2395242A1|1979-01-19|
    IT7824861D0|1978-06-22|
    CS207627B2|1981-08-31|
    AR218495A1|1980-06-13|
    DE2826865C2|1989-03-09|
    JPS549232A|1979-01-24|
    BR7803953A|1979-01-16|
    JPS6132294B2|1986-07-25|
    AU519785B2|1981-12-24|
    IN148867B|1981-07-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3751506A|1972-05-12|1973-08-07|Mobil Oil Corp|Vapor-phase alkylation in presence of crystalline aluminosilicate catalyst|
    US3941871A|1973-11-02|1976-03-02|Mobil Oil Corporation|Crystalline silicates and method of preparing the same|
    US4002697A|1973-12-03|1977-01-11|Mobil Oil Corporation|Selective production of para-xylene|
    US4016218A|1975-05-29|1977-04-05|Mobil Oil Corporation|Alkylation in presence of thermally modified crystalline aluminosilicate catalyst|
    NZ183608A|1976-03-31|1978-12-18|Mobil Oil Corp|Aluminosilicate zeolite catalyst for selectine production of para-diakyl substituted benzenes|
    DE2622318C2|1976-05-19|1986-01-02|Mobil Oil Corp., New York, N.Y.|Process for the alkylation or transalkylation of aromatic hydrocarbons|
    US4086287A|1976-07-19|1978-04-25|Mobil Oil Corporation|Selective ethylation of mono alkyl benzenes|US4086287A|1976-07-19|1978-04-25|Mobil Oil Corporation|Selective ethylation of mono alkyl benzenes|
    DE2961498D1|1978-05-08|1982-01-28|Ici Plc|Production of xylene hydrocarbons|
    CA1135286A|1978-12-14|1982-11-09|Mobil Oil Corporation|Alkylation of aromatic hydrocarbons|
    US4205053A|1979-02-01|1980-05-27|Mobil Oil Corporation|Manufacture of nitrogenous zeolites|
    US4229424A|1979-04-09|1980-10-21|Mobil Oil Corporation|Crystalline zeolite product constituting ZSM-5/ZSM-11 intermediates|
    CA1140161A|1980-04-28|1983-01-25|Bernard F. Mulaskey|Hydrocarbon conversion with crystalline silicates|
    US4490570A|1982-02-22|1984-12-25|Cosden Technology, Inc.|Method for para selective alkylation employing silicalite catalysts|
    US4520220A|1982-02-22|1985-05-28|Cosden Technology, Inc.|Alkylation of aromatics employing silicalite catalysts|
    US4400570A|1982-05-21|1983-08-23|Cosden Technology, Inc.|Ethylbenzene production employing tea-silicate catalysts|
    US4447664A|1982-09-23|1984-05-08|The Dow Chemical Company|Integrated Fischer-Tropsch and aromatic alkylation process|
    JPS6365604B2|1982-12-30|1988-12-16|Asahi Chemical Ind|
    JPH0427957B2|1984-06-29|1992-05-13|Nippon Petrochemicals Co Ltd|
    JPH07679B2|1985-12-05|1995-01-11|三井東圧化学株式会社|Method for copolymerizing ethylene and α-olefin|
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    WO1989007586A1|1988-02-19|1989-08-24|Mobil Oil Corporation|Process for the production of gasoline from fuel gas and catalytic reformate|
    ES2100547T3|1992-06-05|1997-06-16|Mobil Oil Corp|ETHYLTOLUENE PRODUCTION.|
    CA2518470C|2003-03-21|2010-09-21|Stone & Webster, Inc.|Production of alkyl aromatic compounds with catalyst reactivation|
    JP2010229104A|2009-03-27|2010-10-14|Mitsubishi Chemicals Corp|Method for producing alkyl aromatic compound|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/809,510|US4104319A|1977-06-23|1977-06-23|Ethylation of mono alkyl benzene|
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