Process for producing acetic of phenolacetic acid

专利摘要:
A method for producing acetic acid or phenolic acid acid by carbonylation of the corresponding alcohol with carbon monoxide in the presence of methyl iodide or iodine and nickel in the liquid phase at 180-200 ° C and a total pressure of atm, characterized in that, in order to increase the process efficiency and simplify the process, carbonylation leads to medium of acetic acid, constituting 30-90% of the volume of the initial reaction mass, in the presence of vanadyl bisacetylacetonate or vanadium pentoxide, the atomic ratio of which to nickel is 0.25-5, and aci per liter of the reaction mass and CO modistogo nickel bromide or iodine g 160-800 mg-atoms and 0, 0 mol, respectively.
公开号:SU1042610A3
申请号:SU813277447
申请日:1981-05-04
公开日:1983-09-15
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 carboxylic acids, i.e. acetic acid or phenylacetic acid, which find various uses in various areas of chemical production. A known method of producing acetic acid by carbonylation of methanol at a pressure of 700 atm in the presence of nickel complexes resulting from the reaction of nickel halides with halide compounds is readily substituted ammonium (or phosphonium) 1, the complexes have the general formula A4M NiX4 where X is bromine or iodine; M phosphate or nitrogen atom; A is a lower alkyl radical. These complexes are marketable products, although if necessary they can be obtained in advance before the process, since an elevated pressure is used in the carbonylation reaction (about 700 atm, the performance of the catalytic system is low. Performance can be significantly increased if used in on the one hand, the nickel halide compound, and, on the other hand, the methyrechiesied ammonium or phosphonium halide compound in an amount greater than that required to form These formulas are in accordance with stoichiometry 2. However, in this case, high pressures are also used that complicate the technological process. The closest to the invention in technical essence is the method of obtaining, for example, acetic acid by carbonylation of methanol with less harsh conditions, i.e., gfy atm pressure and temperature of 180-200 ° C in the presence of a catalytic system: nickel, free phosphine and / or in a complex with nickel, and at least 10 mol of methyl iodide per 100 mol of methanol Gz1. - - However, the performance of such a system is not high (cf, comparative example). The purpose of the invention is to increase the productivity of the process and to simplify it. The goal is achieved by the method of producing acetic or phenylacetic acid by carbonylation of the corresponding alcohol with carbon monoxide in the presence of methyl iodide or iodine and nickname. l in the liquid phase at a temperature of 180200 ° C and a total pressure of atm, carbonylation is carried out in an acetic acid medium of 30-90 from the volume of the initial reaction mass, in the presence of vanadyl bisacetylacetonate or vanadium pentoxide, the atomic ratio to nickel is 0 , 25-5) and the concentration per liter of the reaction mass of nickel and methyl iodide or iodine is 160-800 mg-atoms and 0.8-, 0 mol, respectively. The nickel used in the process can be in different forms, for example, in the form of Rene nickel or in the form of a compound, for example, acetate, carbonyl, etc. These carbonylation regimes allow using not only pure carbon monoxide, but also carbon monoxide containing hydrogen. In addition, the proposed method makes it possible to simplify the process for estimating the exclusion of phosphines, and using vanadium compounds to increase the efficiency of the process in terms of increasing conversion and productivity. In the examples, the following conventions are used: AcOH is acetic acid; Acome - methyl acetate; AcOH + AcOMe - AcOH is the number of the initial col. + The initial quantity. RR, the molar ratio of acetic acid formed to the initial amount; t is the time of absorption of carbon monoxide at the temperature of the experiment; PI - productivity, in g / h, acetic acid per liter of initial reaction mixture. Example 1. In an autoclave from material, hastelloy B 2, with an osteum of 125 ml 07 mmol of methanol (17 ml), 33 mmol of acetic acid (23 ml), 131 mmol of methyl iodide (8 ml), 10 mg of vanadium atoms in the form of vanadyl bisacetylacetonate ( 2, b5 g). 8 mmol of tetrahydrated nickel acetate (2 g). Next, the reactor is closed and in it pressure in O atm is supplied with carbon monoxide, stirring is carried out. The temperature in the autoclave is maintained for approximately 20 minutes at a level using a ring kiln. The pressure at this moment is reduced to 68 atm. Then it is maintained at a level of 70 atm by supplying pure CO. After completion of the absorption of carbon monoxide after 75 minutes, the heating is continued for another kS min., The same temperature is maintained (200 ° C). After that, the stirring and heating are stopped, the reactor is cooled and degassed. The resulting reaction mixture after dilution analysis 1 is chromatographed using ra3OBovi chromatography; it contains g of acetic acid (RR 6), and no methyl acetate is detected. Productivity (Pj) of the reaction with respect to acetic acid is 330 g / lH. Examples 2-9: Similar to Example 1. A series of experiments was carried out with a reaction mixture containing methanol, acetic acid, nickel, vanadyl bisacetylacetonate. The total duration of the experiment 2h. Specific reaction conditions, as well as the results obtained are shown in Table. 1 and 2. In the control experiment (a) the process was carried out without vanadium, (b) the process was carried out without loading acetic acid.
In the experiment, mg-atoms of vanadium are used, in total
Duration 2 h 35 min.
In the experiment, use Q mmol iodine (instead) and partial
hydrogen pressure of 30 atm (take hydrogen oxide
carbon). Absorption of carbon monoxide was not observed; other indicators were not determined. As can be seen from the data table. 1 and 2, in the absence of acetic acid, carbon monoxide absorption does not flow. Moreover, the vanadium content in the system used affects the productivity of the process. Example 10. Analogously to Example 1, an experiment was carried out with a mixture containing 25 ml (232 mmol) of benzyl alcohol, 15 ml of acetic acid, 161 mmol of methyl iodide, 8 mg atoms of nickel in the form of tetrahydrated nickel acetate, and 40 mg of vanadium atoms in the form of bisacetylacetonate vanadyl reaction temperature. The total pressure is maintained at 60 atm with the supply of pure CO. After 1 h 30 min of reaction at the indicated temperature, 15.8 g of phenylacetic acid (RR i4B%) are obtained. Example 11 The process is carried out analogously to example 1, but tQ mmol of potassium iodide is added to the mixture. The absorption of carbon monoxide is stopped 90 minutes after the start of the reaction, which proceeds at 2QQ ° C. Then the heating at the same temperature is continued for another 30 minutes The total duration of the experiment
Table 2 in experiment S, therefore 2 hours. Received grams of acetic acid; methyl acetate is not formed (RR 6E% and P3 300 g / Cl). 12, Comparative Example according to method 3j. In a & toklava from hastello 82 with a capacity of 125 ml load: 3 ml of methanol (mmol); 19 ml methyl acetate (mmol); 17.5 ml of methyl iodide (330 mmol); 8 mmol triphenylphosphine; 21 mmol & triphenylphosphine / nickel dicarbonyl. After the autoclave is closed, a hydrogen pressure of 15 atm and approximately 25 atm of carbon monoxide is established; the process is carried out with stirring and at a certain temperature for about 20 minutes. The pressure in the autoclave is 60 atm and maintained at this level by the supply of carbon monoxide. After an hour of reaction, stirring and heating are stopped at the indicated temperature, the autoclave is cooled and the gas is removed, and the reaction mixture is analyzed. Results and particular conditions are given in Table. 3, 7 Ta lb a3 OnbiTlTeMnepaTypa / CI RR, | Р 111 1150 30 398.7 23 229 О 2107.5 7.7 Qk26W8 is 23, while As can be seen from these data, at a temperature and a pressure of 60 atm. RR by a known method (see Table 2, 5, experiment 6), B9, productivity 229 g / lh against 590 g / lh in the proposed method.

权利要求:
Claims (1)
[1]
METHOD FOR PRODUCING ACETIC OR PHENYLUXE ACID by carbonylation of the corresponding alcohol with carbon monoxide in the presence of methyl iodide or iodine and nickel in the liquid phase at 180-200 ° С and total pressure of 35150 atm, characterized in that, in order to increase the productivity of the process and its of simplification, carbonylation is carried out in an acetic acid medium, comprising 30-90% of the initial reaction mass, in the presence of vanadyl bisacetylacetonate or vanadium pentoxide, the atomic ratio of which to nickel is 0.25-5, and the concentration per liter of reaction mass of nickel and methyl methyl or iodine 160-800 mg atoms and 0.84.0 mol, respectively.
✓ * ° »sy.ш 1042610>

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同族专利:

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JPS5736269B2|1982-08-03|

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US4436889A|1984-03-13|

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AT3850T|1983-07-15|

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FR2484403B1|1982-07-02|

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JPS572235A|1982-01-07|

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ES8202778A1|1982-03-01|

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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US1946256A|1932-06-28|1934-02-06|Du Pont|Preparation of carboxylic acids|

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US2650245A|1949-04-08|1953-08-25|British Celanese|Synthesis of acetic acid from co and methanol|

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US4133963A|1975-11-19|1979-01-09|Eastman Kodak Company|Process for the production of carboxylic acids|

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US4356320A|1976-11-08|1982-10-26|The Halcon Sd Group, Inc.|Preparation of carboxylic acids|JPH0137575Y2|1982-03-15|1989-11-13|

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JPS59162846U|1983-04-18|1984-10-31|

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US8324413B2|2008-12-23|2012-12-04|Texaco Inc.|Low melting point triglycerides for use in fuels|

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US8361172B2|2008-12-23|2013-01-29|Chevron U.S.A. Inc.|Low melting point triglycerides for use in fuels|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR8010540A|FR2484403B1|1980-05-06|1980-05-06|

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