• 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:
    1491750 Methacrolein by oxidation NIPPON KAYAKU KK 11 Nov 1975 [27 Nov 1974 46564/75 Heading C2C [Also in Division B1] Methacrolein is produced by the gas phase oxidation of isobutylene and/or tert-butyl alcohol with molecular oxygen in the presence of a catalyst of formula wherein J=K, Rb and/or Cs; and for h=12, a=1-15, b=0À3-8, c=0À1-7, d=0À1-3, e=0À01-1, f=0-5, g=greater than 0-1 and i=38-92. The oxidation may be effected at 250-500‹ C., a litre hourly volume space velocity of 360-36,000 and a pressure of 0À5-10 atmospheres using a feed of molar proportions isobutylene/tert-butyl alcohol = oxygen = steam of 1=(0À5-8)=(1-20). The oxygen may be used as air or otherwise diluted with nitrogen or carbon dioxide. The reaction may be carried out in a fluidized or fixed bed.
    公开号:SU1082308A3
    申请号:SU752193155
    申请日:1975-11-26
    公开日:1984-03-23
    发明作者:Сикакура Есихиса；Сакаи Фумио；Симизу Хитоси
    申请人:Ниппон Каяку Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the production of catalysts for the oxidation of organic compounds. A catalyst is known for the oxidation of unsaturated hydrocarbons, for example, isobutylene to methacrolein containing oxides of molybdenum, vanadium and phosphoric anhydride. Closest to the present invention is a catalyst 2 for the oxide of NJL isobutylene or tertiary butyl. the alcohol in methacrolein, including iron, cobalt, bismuth molybde, nickel, oxygen, and metal, is selected from the group containing potassium, rubidium cesium. In addition, the catalyst may contain phosphorus, mouse k. The catalyst in its composition corresponds to the following empirical formula LgH ,, MojO. (With Fe where f 12; b 0–15; 2–15 | C 0.5–7; d 0, 1–4; e 0–4; L 0.01–1 L is phosphorus; H - potassium, rubidium or cesium However, the known catalyst has insufficient activity in the oxidation of isobutylene 1-shea tertiary butyl alcohol.The purpose of the invention is to increase the activity of ataligor i The said goal is 1%, but the catalyst for the oxidation of isobutylene or tertiary butyl alcohol metacropei1-g, hlyuchaschky peso, cobalt bismuth, iolioden, and etallé selected oxygen cell from the group containing kasht, rubidium cesium, additional contains boron and antimony or boron 5 antimony and nickel .. in this case, the catalyst corresponds to the empirical formula Coa 1e B i J. In Sb e I p- Mo p or Co, Fet.Bi, .... ,,, Ni ,, 0 where "1-15; L 0.3-8; with 0.1-7 d OJ-3; e 0.01-1; §- 0.01-1; Ü 12 t - ii, Vj; I - i.2,5-66,7; J; AL57Y I.PI PuPM;., ;; (;:, ..:; 1 i V :( K: For the preparation of the proposed catalyst: Useful and personal combinations of basic elemets. Examples of cobalt mixtures I-KJ are cobalt nitrates; : .ar cobigiu bonates, cobal oxalates1: ha and others, iron mixtures - nitrate iron, iron carbonates iron oxalates and others, nickel nitrate mixtures nickel nitrate, nickel carbonate, nickel oxalate and others, vimmut compounds - bismuth nitrates and other boron compounds - boric acid and others, compounds of potassium, rubidium and desi - the corresponding nitrates are carbonates, hydroxides and others, and molybdenum compounds - ammonium molybdate, molybdic acid, molybdenum trioxide and others. Although the yield is high enough, even when the catalyst is used without any carrier, it may be supported on the carrier. Examples of such carriers suitable for use 5 are silica gel, silica sol, diatomaceous earth, alumina, carborundum, and others. The proposed catalyst may be applied as a fixed, fluidized, or moving word. As a typical example of; -io-leocular oxygen, scd3p is taken; gx It can also be ispsg. :.;: otovan: :: oko pure oxygen or C PiH8pT gas, such as nitrogen.) carbon dioxide or others .; as i-a .-; - bavitel, Reagent (isobutylene or tert-butyl butyl alcohol) is in the / az phase. Preferably, for use in blending the mixture. The feed mixture, which is supplied by the MO to the reaction zone, consists of a tertiary butyl ring, polar oxygen and. For my reaction, the relative proportions of these components are not positive. The preferred mol5 {rnog is the ratio of isobutylene, tertiary alcohol, oxygen and steam in s. is 1: (0.5-8): (1-20), in -IS.CTNosti 1: (1.5-5) :( 2-8), in the case that smoked isobutylene and tertiary butyl are used alcohol n as a reagent, isobutylene and tertiary butyl alcohol can be sour cream in any desired and not limited ratio with excellent results. The gaseous feed mixture can be supplied at any desired space velocity, preferably at a space velocity of about 3,636,000 liters of gas / liter of catalyst-hour, preferably 720-10,800 liters of gas / liter of catalyst.
    the number of moles of reactive isobutylene and / or tertiary butyl alcohol
    reaction%
    the number of moles of isobutylene and / or tertiary butyl alcohol supplied
    the number of moles of methacrolein produced
    Selectivity,%
    the number of moles of reactive psobutylene and / or tertiary butyl alcohol
    the number of moles of methacrolein produced
    Single yield,%
    the number of moles of isobutylene and / or tertiary butyl alcohol
    gas supply flow rate, l gas / h
    Volume velocity volume under KG The flow rate was calculated under normal temperature and pressure conditions, Example 1. 42.4 g of ammonium p-molybdate was dissolved in distilled water, then 0.28 g of potassium nitrate was added. With this stirring, an aqueous solution containing 40.8 g of cobalt nitrate, an aqueous solution containing g of iron nitrate, a dilute solution of nitric acid containing 9–7 g of bismuth nitrate, an aqueous solution containing 2.48 g of boric acid, and an aqueous solution containing g of nickel nitrate and 0.58 g of antimony tri-Si b. 19.5 g of silica gel is then added to the pasty suspension, which is accompanied by a re (mixing -. Then this suspension is evaporated to a dry residue. Crude
    100
    . 100
    100 084 The value of timeline for hindering this reaction is not critical. This reaction may preferably be performed at a temperature in the range of about 250-500 ° C, desirable, but 270-A50 ° C. This reaction may be performed at atmospheric pressure or at or below atmospheric pressure, preferably at atmospheric pressure. Pressure interval 0.5-10 , 0 atm). In the examples, the terms reaction rate, selectivity, single, yield, and volume velocity are defined as; o catalyst, l product is laid in a mold and then calcined at 650 ° C for 6 hours. This product (catalyst A) has the following composition: Co, Res Bi, B Ni.,. The reaction flask with an internal diameter of 21 mm is filled with 40 ml of catalyst A A gas mixture consisting of 1 mol of isobutylene, 12.4 mol of air, 8 mol of steam at a volumetric rate of about 1500 liters of gas / l of catalyst 4s is fed to this reaction tube, and the reaction temperature is: - 250 ° C the reaction of isobutylene is 98.5%, the selectivity of methacrolein is 82.6%, single 81.4% yield of methacrolein and methacrylic acid yield single 1.2%. Correspondingly, the total yield of useful products, taken as the sum of single outputs of methacrolein and methacrylic acid, reaches 82.6%. Although this reaction is performed continuously for a period of about 300 hours, no deterioration in the quality of this catalyst has been found. EXAMPLE 2 The technology of Example 1 is repeated except that 0.41 g of rubidium nitrate is used instead of 0.28 g of calcium nitrate. The resulting product (catalyst S) has the following composition: Co FejBi, ff6, T The oxidative reaction was performed using catalyst B in the same manner as described in Example 1. The results are summarized in Table 2. 1 and 2 „
    T and l and ts, and 1 8fe Primerz. The technology of example 1 is repeated except for the genius: that using, sweat Oj54 g of nitrate, instead of Oj 28 g of potassium nitrate. The semi-finished product (catalyst C) has the following composition: Co.FejBi, 7 The oxidative reaction is performed using catalyst C in the same manner as described in Example 1. The results are summarized in Table 2. 1 and 2.. Example 4-16. Ilpji performance 3 described in examples 1-3, the technology obtained a series of catalysts; having the composition shown in Table 1. Each of the catalysts used for the oxidation of isobutylene in the same manner as described in example 1. The results are given in table. 1 and 2,
    73

    ten
    4.5
    2 1 2 3
    5 6
    3
    0.1 0.1
    SI
    0.2
    0.7
    0.1
    0.1
    0 „06
    0.2
    0.1
    0.1
    0.1
    0.1
    1082308
    ten
    Continued table. 2 Example 33. A gas mixture consisting of O2 mol of isobutylene, 0.8 mol of tert-1-n-butyl alcohol, 12.4 mol of air, 8 mol of steam at: a high speed of 1500 l of gas / l of catalyst-h, and the reaction temperature is maintained at about 340 ° C. The total reaction rate of isobutylene and tertiary butyl alcohol is 99.0%, the selectivity of methacrolein is 82.7%, the single output of methacrolein is 81.9%, the single output of metacryhyl acid 1.0%, the total yield of useful products is 82.9%, EXAMPLE 3. In the reaction flask j loaded with catalyst B, a gas mixture consisting of C, 5 mol of isobutylene, 0.5 mol of one third, is poused. butyl alcohol, 12.4 mol in the spirit and 8 mol of vapor at a volumetric rate of about 1500 l of gas / l of catalyst-h, and the reaction temperature is maintained at 345 ° C. The full reaction rate of isobutylene and tertiary butyl alcohol is continued. Table. 3, 99.3%, methacrolein selectivity 86.2%, single methacrolein yield 85.6%, single methacrylic acid yield 1.1%, and the total yield of useful products 86.7%. Example. Comparative. The technology of Example 2 is repeated except that no antimony trioxide is added. The resulting product (catalyst B) has the following composition. Co. ,, The oxidation reaction is carried out using catalyst B in the same manner as described in example 1. In this example, the reaction temperature is maintained at. The reaction rate of isobutylene is 97.8%, the selectivity of methacrolein is 77.2%, the single yield of methacrolein is 75.5%, the single yield of methacrylic acid is 0.7%. And the total yield of useful products is 76.2%. Example37. The Q-X catalysts are prepared by the same method as in Example 1 and the same reaction is carried out as in Example 1 using each catalyst from Q to X. Cox is methacrolein. - methacrol acid.
    Tava catalysts are summarized in Table A. The results are summarized in table. five.
    15108230816
    Example 38. Instead of using the isobutylizer from Example 37, as this obin is subjected to oxidation, it is subjected to a tertiary butylum in Example 1. The resulting Alcohol obtained, benefiting each catata, are summarized in Table. about.
    Table 6
    权利要求:
    Claims (2)
    [1]
    The DPA catalyst for the oxidation of isobutylene or tertiary butyl alcohol into methacrolein, including iron, cobalt, bismuth, molybdenum, oxygen and a metal selected from the group consisting of potassium, rubidium, cesium, characterized in that it additionally contains boron activity of the catalyst and antimony or boron, antimony and nickel, while the composition of the catalyst corresponds to the empirical formula
    C ° "F e bBicB s! Sb e or Co tf Fe fc Bi c B d Sb e 1 ^, Mg n Ni b 0. where a = 1-15;
    b = 0.3-8; c = 0.1-7;
    d = 0.1-3; g e = 0.01-1;
    = 0.01-1; b is 12;
    -i = 42.6-66.7 f- 0.5-5;
    [2]
    3- potassium or rubidium or cesium '
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1082308A3|1984-03-23|Catalyst of oxidation of isobutylene or tertiary butanol into methacroleine
    US4219670A|1980-08-26|Process for producing unsaturated aldehydes and unsaturated carboxylic acids
    US4155938A|1979-05-22|Oxidation of olefins
    US4423281A|1983-12-27|Process for producing conjugated diolefins
    US3972920A|1976-08-03|Process for producing unsaturated aldehydes, unsaturated fatty acids or conjugated dienes
    US4336409A|1982-06-22|Process for producing conjugated diolefins
    US4816603A|1989-03-28|Process for the production of methacrolein and methacrylic acid
    US4052450A|1977-10-04|Catalytic oxidation of α-olefins
    US4341900A|1982-07-27|Catalytic process for the preparation of unsaturated carboxylic acid
    US3825600A|1974-07-23|Process for the preparation of unsaturated carbonyl compounds
    US6965046B2|2005-11-15|Catalyst for the manufacture of acrylonitrile
    US4118419A|1978-10-03|Catalytic process for the preparation of an unsaturated carboxylic acid
    US3966823A|1976-06-29|Process for preparing 1,3-butadiene and methacrolein simultaneously
    US4985592A|1991-01-15|Process for the preparation of unsaturated carboxylic acids
    US4111985A|1978-09-05|Process for producing unsaturated aldehydes and unsaturated carboxylic acids
    RU2036888C1|1995-06-09|Method of synthesis of ethylene and/or acetic acid and catalytic composition for its realization
    US4025565A|1977-05-24|Process for preparing unsaturated aldehyde having three to four carbon atoms
    US4354044A|1982-10-12|Method for preparing methacrolein
    US4186152A|1980-01-29|Oxidation of olefins
    US4250339A|1981-02-10|Process for producing methacrolein
    US3907712A|1975-09-23|Catalyst composition for the preparation of unsaturated carbonyl compounds
    US4245118A|1981-01-13|Oxidation of unsaturated aldehydes
    US3998867A|1976-12-21|Process for the simultaneous preparation of methacrylonitrile and 1,3-butadiene
    US4209640A|1980-06-24|Catalysts for the oxidation of unsaturated aldehydes
    US3895051A|1975-07-15|Catalyst and process for oxidizing or ammoxidizing n-butenes and/or isobutene
    同族专利:
    公开号 | 公开日
    JPS5163112A|1976-06-01|
    IT1049889B|1981-02-10|
    FR2292518B1|1978-05-12|
    NL162626C|1980-06-16|
    BE835935A|1976-05-25|
    DE2550962A1|1976-08-12|
    US4012449A|1977-03-15|
    CA1036175A|1978-08-08|
    JPS5347088B2|1978-12-19|
    NL162626B|1980-01-15|
    NL7513228A|1976-05-31|
    FR2292518A1|1976-06-25|
    GB1491750A|1977-11-16|
    DE2550962B2|1977-02-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3446840A|1966-02-24|1969-05-27|Asahi Chemical Ind|Process for the catalytic oxidation of propylene|
    US3642930A|1968-12-30|1972-02-15|Standard Oil Co Ohio|Process for the manufacture of isoprene from isoamylenes and methyl butanols and catalyst therefor|
    BE749305A|1969-05-02|1970-10-01|Nippon Kayaku Kk|OXIDIZATION CATALYST AND ITS USE (|
    JPS4817253B1|1970-11-07|1973-05-28|
    JPS5112603B1|1971-05-26|1976-04-21|
    US3803204A|1972-03-27|1974-04-09|Standard Oil Co|Preparation of aromatic nitriles|
    DE2424934A1|1973-06-04|1975-01-02|Standard Oil Co Ohio|METHOD OF CATALYTIC PRODUCTION OF UNSATATULATED NITRILES|
    JPS5821614B2|1973-07-19|1983-05-02|Nippon Kayaku Kk|US4065507A|1976-08-02|1977-12-27|Standard Oil Company|Preparation of methacrylic derivatives from tertiary butyl-containing compounds|
    CA1127137A|1977-12-20|1982-07-06|Dev D. Suresh|Ammoxidation of olefins with novel antimonatecatalysts|
    US4147721A|1978-04-06|1979-04-03|Halcon Research And Development Corporation|Process for recovering methacrylic acid|
    DE2841712A1|1978-09-25|1980-04-10|Basf Ag|PROCESS FOR THE PREPARATION OF P-SUBSTITUTED BENZALDEHYDE|
    JPS5612331A|1979-07-09|1981-02-06|Sumitomo Chem Co Ltd|Preparation of methacrolein|
    JPS632946B2|1979-09-25|1988-01-21|Asahi Chemical Ind|
    US4414134A|1981-01-05|1983-11-08|The Standard Oil Co.|Impregnating catalysts|
    JPS6236740B2|1982-09-06|1987-08-08|Nippon Shokubai Kagaku Kogyo Kk|
    EP0460932B1|1990-06-06|1995-05-17|MITSUI TOATSU CHEMICALS, Inc.|Method for preparing acrolein or methacrolein|
    JP2841324B2|1990-06-06|1998-12-24|三井化学株式会社|Method for producing methacrolein|
    US7851397B2|2005-07-25|2010-12-14|Saudi Basic Industries Corporation|Catalyst for methacrolein oxidation and method for making and using same|
    US7732367B2|2005-07-25|2010-06-08|Saudi Basic Industries Corporation|Catalyst for methacrolein oxidation and method for making and using same|
    US7649111B2|2005-07-25|2010-01-19|Saudi Basic Industries Corporation|Catalyst for the oxidation of a mixed aldehyde feedstock to methacrylic acid and methods for making and using same|
    US7649112B2|2005-07-25|2010-01-19|Saudi Basic Industries Corporation|Integrated plant for producing 2-ethyl-hexanol and methacrylic acid and a method based thereon|
    US7799946B2|2007-02-14|2010-09-21|Saudi Basic Industries Corporation|Process for separating methacrolein from methacrylic acid in a gas phase product from the partial oxidation of isobutene|
    EP1995232B1|2007-05-25|2018-01-03|Evonik Röhm GmbH|Use of feed compositions in preparation of methacrylic acid by oxidation|
    US8921257B2|2011-12-02|2014-12-30|Saudi Basic Industries Corporation|Dual function partial oxidation catalyst for propane to acrylic acid conversion|
    US8722940B2|2012-03-01|2014-05-13|Saudi Basic Industries Corporation|High molybdenum mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP13556974A|JPS5347088B2|1974-11-27|1974-11-27|
    [返回顶部]