• 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:
    1. THE METHOD OF OBTAINING ACETALEDWGID by bicarbonylation of methanol in the liquid phase at elevated temperature and pressure in the presence of a cobalt-ruthenium-containing catalyst and halogen-containing promoter, which is different because, in order to improve the efficiency of the process, the tool was used by the artist to find a tool that was used by the artist to find a halogen-containing promoter. quaternary ammonium or quaternary phosphonium and the lower haloalkyl, taken in the amount of 11.7-36 mmol / l, and the process is carried out at the molar ratio of halogen nida alkali or alkaline earth metal, or quaternary ammonium or quaternary phosphonium and cobalt 10.6: 1 - 100: 1 atomic ratio of ruthenium and cobalt 0.1: 1 - 0.96: 3 cobalt concentration of 1.15-j - 11.3 mg-atom / l, temperature 185-. , 215c and a pressure of 95-260 atm. 2. Method according to claim 1, characterized by the fact that halomethyl is used as the lower alkyl halide, 3. Method according to claim 1, about tl and h Yusch and with the fact that as the halide of an alkali or alkaline earth metal, or a quaternary phosphonium and as a lower haloalkyl, iodnd is used,: l with |
    公开号:SU1053742A3
    申请号:SU802938262
    申请日:1980-07-01
    公开日:1983-11-07
    发明作者:Готье-Лафайе Жан；Перрон Робер
    申请人:Рон-Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for producing acetaldehyde, which is widely used to produce acetic acid and acetic anhydride.
    A known method for producing acetaldehyde by carbonylation of methanol at 5 ° C at 185 ° C and a pressure of 300-400 atm in the presence of a catalyst is cobalt and halogen and the cobalt concentration is less than 2 mmol per 1 mole of methanol. Productivity; process agility is. 10 70 g of acetaldehyde per hour and per gram of cobalt l}.
    The closest to the proposed technical solution is the method of producing acetaldehyde by hydro tS by carbonylation of methanol in a low phase — at a pressure of 150 atm in the presence of a catalyst — cobalt and ruthenium and methyl iodide in methyl benzoate with a ruthetd or cobalt atomic ratio of 0.057; 1 OD12 : 1,. Cobalt concentration 80 mg atom / l, mol / ratio of kaZ / Co 2.5: l-7/5 l. The productivity of the process in the absence of a ruth is 13.8 g of acetaldehyde per hour and per g of cobalt and 0.8 to 5.7 g of acetal haldehyde in the presence of ruthenium 2 additives,
    A disadvantage of the known methods is the low productivity of the process 30,
    The aim of the invention is to increase the productivity of the process
    Delivered lie eh achieved with a method for producing acetaldehyde 35 gidrokarbonilirovaniom methanol in the liquid phase at 185-215 C and a pressure of 95-260 atmospheres in the presence kobaltrutonyysoderzhaschego catalyst and halogen-containing promoter - 40 halide, an alkali or alkaline earth metal or a quaternary ammonium or quaternary phosphonium, and lower haloalkyl , taken in the amount of 11.7-36 mmol / g, and the process will proceed with the molar assignment of an alkali metal or alkaline earth metal halide, quaternary ammonium, or quaternary phosphon and cobalt 10.6: 1 - 100: 1, the atom ratio of ruthenium and cobalt is 0.1: 1 - O 0.96: 1, the concentration of cobalt is 1.1511, 3 mg-atom / l. As a lower haloalkl use halomethyl „
    As halo alkaline
    or alkaline earth metal, or quaternary phosphonium, and odide is used as the lower haloalkyl. .
    The source of cobalt can serve as a finely distributed metal cobalt, its inorganic salts, ak cobalt carbonate, organic ol, especially fatty acid. Cobalt carbonyls, hydrocarbonyls or their complexes can also be used. The cobalt derivatives, KOTOjxje can be used, cobalt acetate and formate, cobalt halides, especially cobalt iodide, dicobalt octacarbonyl.
    Ruthenium uses metallic in a finely distributed form or its compounds, for example, RuCi, RuJ, EuOq, RujtCOl, Ru, (CjHyOy%.
    The hydrocarbonylation of the proposed method is carried out in the liquid phase. Since it is most often operated with an excess of methanol, the simultaneous use of an additional solvent is unnecessary, but solvents such as hydrocarbons / esters, ethers, and reaction products can be used.
    According to the proposed method, there is no need to pre-clean or dehydrate methanol. You can use technical grade methanol containing, for example, water.
    Methanol is reacted with a mixture of carbon monoxide and hydrogen. The mixture contains at least 25 mol.% Of hydrogen. Use mixtures containing up to 95% hydrogen, and mainly containing 40-80 hydrogen. The gas mixture may contain impurities such as carbon dioxide, oxygen, methane and nitrogen.
    The method is carried out as follows.
    A stainless steel autoclave Z8-CNDT 7-12 (AFNOR standards) with a volume of 250 MP is loaded with methanol, if necessary, a solvent and components of the catalytic system. (Sources of cobalt and ruthenium, if not otherwise indicated, are dicobaltoctcarbonyl and dodecacarbonyl triruthenium, respectively).
    After the autoclave is closed, an initial pressure is established, the value of which is adjusted using a mixture of the composition indicated for each experiment. The initial components are shifted and the autoclave is brought to the required temperature in approximately 20 minutes using a ring furnace. The pressure in the autoclave is maintained by periodic mixture re-loading. CO / H, the composition of which, unless otherwise indicated, is identical to the composition of the mixture, which serves to establish the initial pressure. After a certain reaction time at the specified temperature, heating and stirring is stopped, the autoclave is cooled and degassed.
    The resulting reaction mixture is diluted and analyzed by gas chromatography.
    The readings g / hl l and (Co) express the productivity of acetaldehyde in grams per hour of reaction, respectively, per liter of reaction volume and per gram of cobalt introduced into the pJ action.
    Example. In the autoclave according to the described principle of operation, 95 ml of methanol, 5 ml of vrg, 509 mg (3.58 mmol) of methyl iodide, 1.8 g (12 mmol) of sodium iodide,, 0.126 mg of cobalt atoms or 21.6 mg of dicobaltoctcarbonyl 0.117 mg-atm ruthenig or 25 mg dodecarbonyl triruthenium. An initial pressure of 140 atm is established using an equimolar CO / H mixture. The autoclave is adjusted to 215 ° C. The pressure in the autoclave is maintained at 230-260 atm by periodic repeated downloads of a CO / H2 1/2 mixture. In 1 hour and 15 minutes of reaction, 24.7 g of acetaldehyde is obtained, its productivity is 200 g / hl l and 2600 g / hg (Co). Control experiment. Reproduce Example 1, lowering the dodecacarbonyl tri-truss. 14.1 g of acetaldehyde are obtained, which corresponds to a productivity of about 110 g / 41 l and 1400 g / FH (Co). In the absence of ruthenium, the performance drops noticeably.
    Control experiment. Using the principle of operation described, 95 ml of methanol, 1.5 ml of water, 3.58 mmol of methyl iodide, 12 mmol / sodium iodide and 0.66 mg-atom of ruthenium in the form of dodecacarbonyl triruthenium are charged. For 1 hour and 30 minutes of reaction at 210 ° C, the pressure in the autoclave is maintained at 230-260 atm by periodic repeated downloads of an equimolecular mixture of CO and Hg2, yielding 19t only 0.7 g of acetaldehyde. ratios: practically does not have any catalytic effect. :
    Comparing example 1 and the control experiment, state the startling effect created by three small amounts of ruthenium added to the catalytic system based on cobalt, and an absolutely unexpected action when considering the negative results obtained in the control experiment b
    Example 2. In a charge formed of 0.123 mg cobalt atoms, 0.113 mg ruthenium atoms, 12 mmol of tetrabutylammonium bromide, 1.5 mmol of methyl iodide and 100 ml of methanol set an initial pressure of 140 atm using a mixture of CO / H2 2/3. After 40 min of reaction at 205 ° C, the pressure in the autoclave is maintained at 245260. Atm, yielding 5.2 g of acetaldehyde. 78% of the converted methanol is converted to acetaldehyde, the main by-products are
    ethanol (0.4 g), methyl oxide and ethyl oxide (0.4 g) and methyl acetate (0.6 g). Productivity is 1070 g / ht (With).
    Froze In a load of 100 ml of methanol, 2.4 mt-yul of ethyl bromide, 0.108 mg of ruthenium atoms, 11 mmol of lithium iodide and 0.120 mg of cobalt atoms, the initial pressure of 140 atm is set using a mixture. After 40 min of reaction, the pressure in the autoclave is maintained at 185-245 atm, and 10.1 g of acetaldehyde is obtained. 84 mol of methanol was converted to acetaldehyde. The productivity was 2000 g / h, g (Co).
    Example 4. In a charge formed of 0.130 mg-Cobalt atoms, 0.125 mg ruthenium atoms, 12 mgl of triphenylmethylphosphonium iodide, 1.6 mmol of methyl iodide and 100 ml of methanol, an initial pressure of 140 atm is set using a mixture of CO / H, 2-2 / 3. After 40 min of reaction at 205 ° C, the pressure in the autoclave is maintained at 230-260 atm, producing 19.5 g of acetaldehyde. Performance: 290 g / hl and 3800 g / hg (Co). 84 mol.% Converted methanol turned into acetaldehyde. The presence of ethanol below 1 g is observed.
    1. Example 5. In the load, formed with 100 vji methanol, l, l7 chio: ethyl iodide, 12 mmol sodium iodide, 0.116 mg rut atoms and 0.128 mg cobalt atoms, establish an initial pressure of 140 atm using an equimolecular CO / H mixture. For 40 min of reaction at 205c, the pressure in the autoclave is maintained at 230-260 atm, 20.7 g of acetaldehyde are obtained. The throughput is 310 g / CL and 4100 g / h g- (With 81 mol.% Of the converted methanol is converted to acetaldehyde.
    Example 6. In a charge formed of 0.126 mg cobalt atoms, 0.121 mg ruthenium atoms, 12 mmol of sodium iodide, 1.72 mmol of methyl iodide and 100 ml of methanol, establishes an initial pressure of 140 atm using an equimolecular CO / H2 mixture. After 1 hour and 15 minutes of reaction at 215 ° C, the pressure in the autoclave is maintained at 230-260 atm, and 27.7 g of acetaldehyde are obtained. 73 mol.% Converted methanol turned into acetaldehyde. Productivity is 3000 g / ht (Co).
    Examples 7-11. In a batch containing 100 ml of methanol, 12 mmol of tributylmethylphosphonium iodide, methyl iodide, dicobalt octacarbonyl and triruthenium decarbonyl, set an initial pressure of 70 bar for examples 10 and 11 and 40 bar for other examples, as well as for control
    Experience with, help the mix. The reaction time at 205 ° C is 40 minutes, the pressure in the autoclave is maintained at 140-155 atm for examples 10 and 11 and 95-105 atm for other examples, as well as for the control experiment C.
    The conditions and the results obtained are given in ha6l.1. ,, .-.
    In all cases, 80-90 mol% of the converted methanol was converted to acetaldehyde. Individual
    the catalytic system produces remarkable results despite the small pressures used.
    The molar ratios of metal halide, ammonium, phosphonium, and cobalt, the Ru / Cb atomic ratio, and the cobalt concentration are presented in Table 2.
    The proposed method allows to increase the productivity of the process up to 1070-300 g / h g (Co) against 5.7-13.8 g / h "g (Co) according to a known method.
    Table 1
    权利要求:
    Claims (3)
    [1]
    1. METHOD FOR PRODUCING ACETAL DEHYDE by hydrocarbonylation of methanol in the liquid phase at elevated temperature and pressure in the presence of cobaltruthenium-containing catalyst and a halide-containing promoter, characterized in that, in order to increase the productivity of the process, an alkali or alkaline earth metal halide is used as a halide-containing promoter. or quaternary phosphonium and lower halogenated, taken in an amount of 11.7-36 mmol / l, and the process is carried out at a molar ratio of halide h metal or alkaline earth metal, or quaternary ammonium or quaternary phosphonium and cobalt 10.6: 1 - 100: 1 atomic ratio of ruthenium and cobalt 0.1: 1 - 0.96: 1, the concentration of cobalt 1.15-. ·. . · 11.3 mg-atom / l, a temperature of 185215 ° C and a pressure of 95-260 atm.
    [2]
    2. The method according to claim 1, characterized by the fact that, as the lower alkyl halide, halomethyl is used. L
    [3]
    3. The method according to claim 1, with the exception of the fact that as an alkali metal or alkaline earth metal halide or quaternary phosphonium halide and iodide is used as lower haloalkyl.
    ; 1053742
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2727902A|1951-12-18|1955-12-20|Basf Ag|Process for the production of aliphatic oxygen compounds by carbonylation of alcohols and ethers|
    US2729651A|1952-06-11|1956-01-03|Basf Ag|Process for the production of aliphatic oxygen compounds by carbonylation of alcohols, ethers, and esters|
    US3248432A|1961-12-12|1966-04-26|Commercial Solvents Corp|Process for the production of ethyl alcohol|
    US3356734A|1963-02-28|1967-12-05|Kuraishi Michio|Process for the production of acetaldehyde|
    US3285948A|1965-01-22|1966-11-15|Commercial Solvents Corp|Halides of ruthenium and osmium in conjunction with cobalt and iodine in the production of ethanol from methanol|
    JPS482525U|1971-05-24|1973-01-12|
    BE842430A|1975-06-09|1976-12-01|PROCESS FOR PREPARING ETHANOL FROM METHANOL, CARBON MONOXIDE AND HYDROGEN|
    US4190729A|1977-09-19|1980-02-26|Monsanto Company|Carbonylation process with stabilized catalyst|
    CA1094105A|1977-11-08|1981-01-20|Brian R. Gane|Process for the production of acetaldehyde by the reaction of methanol with synthesis gas|
    US4133966A|1977-12-23|1979-01-09|Gulf Research & Development Company|Selective formation of ethanol from methanol, hydrogen and carbon monoxide|
    US4151208A|1977-12-23|1979-04-24|Gulf Research & Development Company|Process for the selective preparation of acetaldehyde from methanol and synthesis gas|
    US4126752A|1978-03-06|1978-11-21|Allied Chemical Corporation|Homologation of methanol with a carbon monoxide-water mixture|
    US4171461A|1978-09-01|1979-10-16|Air Products And Chemicals, Inc.|Synthesis of ethanol by homologation of methanol|
    FR2441603B1|1978-10-31|1981-05-29|Rhone Poulenc Ind|
    US4233466A|1979-11-15|1980-11-11|Union Carbide Corporation|Homologation process for the production of ethanol from methanol|US4348541A|1979-11-30|1982-09-07|Exxon Research And Engineering Company|Methanol homologation using cobalt-ruthenium catalysts|
    CA1155458A|1980-04-09|1983-10-18|Union Carbide Corporation|Process for the selective hydroformylation ofmethanol to acetaldehyde|
    JPS6326094B2|1980-06-18|1988-05-27|Mitsubishi Gas Chemical Co|
    DE3031558C2|1980-08-21|1984-04-26|Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln|Process for the production of acetaldehyde and ethanol|
    DE3045891C2|1980-12-05|1983-03-03|Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln|Process for the production of acetaldehyde and ethanol|
    US4433176A|1982-02-01|1984-02-21|Texaco Inc.|Process for preparing acetaldehyde from methanol and synthesis gas using a novel catalyst composition|
    US4433177A|1982-02-01|1984-02-21|Texaco Inc.|Process for preparing acetaldehyde from methanol and synthesis gas using a novel catalyst composition|
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    US4628121A|1985-09-27|1986-12-09|The Halcon Sd Group, Inc.|Preparation of acetaldehyde|
    US4954665A|1985-11-07|1990-09-04|Union Carbide Chemicals And Plastics Company Inc.|Methanol homologation|
    US4993298A|1989-10-04|1991-02-19|Alpha Industries, Inc.|Apparatus for mounting a notching blade|
    US20050154239A1|2004-01-08|2005-07-14|Windhorst Kenneth A.|Methods for preparing 1,3 butylene glycol|
    US9266806B1|2014-12-30|2016-02-23|Eastman Chemical Company|Reductive carbonylation of methanol to acetaldehyde|
    US9714206B2|2014-12-30|2017-07-25|Eastman Chemical Company|Methyl-iodide-free carbonylation of an alcohol to its homologous aldehyde and/or alcohol|
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    US9238606B1|2014-12-30|2016-01-19|Eastman Chemical Company|Methyl-Iodide-free carbonylation of methanol to acetaldehyde|
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    法律状态:
    优先权:
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