• 专利附录
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    • 专利摘要:
    1. Process for the preparation of a monocarboxylic acid by carbonylating an alcohol, in the liquid phase, at a temperature between 120 and 240 degrees C, in the presence of an effective amount of nickel, characterised in that the reaction is carried out under a partial pressure of carbon monoxide which is less than or equal to 150 bars, in the simultaneous presence of at least one alkali metal halide or alkaline earth metal halide, at least one alkyl halide and a solvent chosen from the group comprising tetramethylenesulphone, its derivatives obtained by replacing one or more hydrogen atoms by alkyl radicals containing from 1 to 4 carbon atoms, polyethylene glycol alkyl ethers of the formula R**1 -O-(CH2 -CH2 -O)m -R**2 in which R**1 and R**2 , which are identical or different, represent an alkyl radical containing from 1 to 4 carbon atoms and m is an integer which can vary from 1 to 8 (1 =< m =< 8), and the compounds of the formula see diagramm : EP0018927,P12,F1 in which R**3 , R**4 and R**5 , which are identical or different, represent a linear or branched alkyl radical, a cycloalkyl radical, an aralkyl radical or a monocyclic aryl radical, the said radicals having at most 10 carbon atoms, it being possible for two of the radicals R**3 , R**4 or R**5 together to form a single divalent radical -(CH2 )n -, being an integer between 3 and 12 (3 =< n =< 12), and it also being possible for R**3 to represent hydrogen or a radical see diagramm : EP0018927,P13,F1 in which R**6 and R**7 , which are identical or different, represent an alkyl radical having from 1 to 4 carbon atoms.
    公开号:SU1026650A3
    申请号:SU802912053
    申请日:1980-04-23
    公开日:1983-06-30
    发明作者:Готье-Лафайе Жан；Перрон Робер
    申请人:Рон-Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    2. The method according to p. 1, is different from the fact that iodide GI - € 4 is used as a haloalkyl.
    3. The method according to claim 1, characterized in that iodide is used as the alkali metal or alkaline earth metal halide.
    The invention relates to a process for the preparation of carboxylic acids, in particular acetic acid, by carbonylation of alcohol. Acetic acid can be obtained by carbonylation of methanol under relatively harsh conditions in the presence of nickel and free or bonded halogen. A known method of producing acetic acid by carbonylation of methanol in the presence of nickel complexes obtained by the reaction of nickel halides with even, vertical ammonium (or phosphonium) halides of the general formula. A. where X is bromine or iodine; f is phosphorus or nitrogen; And - for example, the radical of lower alkyl. The complexes are introduced into the re; action in the specified form; l. However, although the pressure during the carbonylation reaction is increased (on the order of 700 atm1, the efficiency of the catalytic system is very small (about 30 g / day) in the calculation of the sum of the acetic acid and methyl acetate. Performance; expressed either in relation to the reaction volume, or in relation to the use of my mass of nickel, it can be significantly improved by introducing into the reaction nickel halide and quaternary ammonium halide (or phosphonium) in quantities exceeding the quantities that the stoichiometry requires to form complexes of the indicated form However, even in this case, the process is carried out at a very high pressure. Catalytic systems are known, which allows the carbonylation of methanol to be carried out under less severe pressure conditions. The method for the production of acetic acid by means of methanol is closest to the proposed technical essence. the presence of at least 10 mol of methyl methyl per 100 mol of methanol, nickel and free and / or nickel bound frsphine at a pressure below 70 atm SJ. However, the efficiency of such a system is small (about 200 g / hl). In addition, the known Method is characterized by instability, high cost due to the use of expensive phosphines and requires the use of corrosion-resistant equipment due to the presence of large amounts of methyl iodide. . The purpose of the invention is to increase the productivity of the process and simplify it by eliminating phosphines and reducing the amount of halogen alkyl used. The objective 1a is achieved by the fact that according to the method of producing monocarboxylic acids of the general formula R-COOH (I) where R is methyl, ethyl or benzyl, by hard-phase carbonylation of the alcohol of general formula R-OH. (P) where R has the indicated values, at 150-210 ° C, the partial pressure of carbon monoxide is 20-140 atm using a nickel-containing catalyst in an amount of 50-320 mg-at. nickel per 1 liter of the reaction mixture in the presence of haloalkyl, the process is carried out in the presence of an alkali or alkaline earth metal halide in a solvent selected from the group consisting of tetramethylene sulfone, tetraglyme, N, M-di (CjC alkyl) - acetamide, L, L-dibutylformamide, N, N-diethyltoluolamide, N- (alkyl) -pyrrolidone, N-methylpiperidone, when the volume ratio of alcohol solvent is 1: 0.4-4, with a ratio of haloalkyl to nickel equal to I-IO mol / g-at, and halogenations of alkali or alkaline-earth metal to nickel equal to 1-10; / or / G, and% B are used as the haloalkyl iodide, alkyl. As the alkali metal or alkaline earth metal halide, iodide is used. - The system allows to work at temperatures higher and, therefore, to achieve increased hourly productivity, to eliminate the period of initiation of the reaction, to operate at low partial pressure of carbon monoxide and with a limited amount of alkyl halide, thus reducing equipment corrosion and promoting recycling of the catalytic composition. In addition, carbonylation of methanol to acetic acid yields unsatisfactory results if the partial pressure of carbon monoxide is elevated. ; According to the invention, carbon monoxide is reacted with an appropriate alcohol to obtain the corresponding carboxylic acid, i.e. containing one carbon atom in the molecule more than the original alcohol, according to the following scheme ROH + CO RCOOH where R is predominantly methyl. To carry out the proposed method, it is necessary to use nickel, which can be introduced in the form of methane, for example, Rene nickel) or in any other convenient form. Carbonate, oxide, hydroxide, halogenoids, in particular iodide, and carboxylates can be used as a source of nickel , in particular acetate, and carbonyl nickel. Rene nickel, iodide, acetate and ka: nickel carbonyl are mainly used. The content of nickel, which affects the reaction rate, is determined depending on the reaction rate and in the optimal case is 50 to 300 mg-at. 1 l rast thief. Chloride, bromides and alkaline or alkaline earth iodides can be used as alkaline or alkaline-earth hapogenide, mainly alkaline or alkaline-earth iodides, especially sodium or potassium iodide. The amount of alkaline or alkaline-earth hapogenide can be varied over a wide range, and in the optimal case, this content is 1 to 10 mol of the halide per 1 g-at. nickel present in the reaction medium. In addition, the proposed method requires the presence of a haloalkyl, where the halogen is chlorine, bromine or predominantly iodine. Haloalkyl can be formed from the halogen derivatives, like C8 |, Brg Dj, HC8. HBg, NiBr2, and N132 of Alcohol (starting material}. When the halogenated derivative is chosen among nickel compounds, e can be considered as a source not only of alkyl halide, but also as a source of metal catalyst. In this case, it is preferable to first download the haloalkyl and / or , different from the indicated halides of nel, the invention provides for the use of chlorides, bromides. and yoDyd lower alkyls having 1 4 carbon atoms, such as bromide and methyl iodide, bromide and ethyl iodide and butyl iodide, mainly Odide methyl, iodine or hydroiodic acid. In the optimal case, the amount of halogenated activator is 1-10 mol (in terms of halogen) per 1 g-at. ikel that is present in the reaction medium. To carry out the proposed method, a certain solvent must be used. These solvents can be formed with tetramethylene sulfone and its derivatives, obtained by replacing one or more hydrogen atoms with lower alkyl radicals. It is preferable to use solvents formed by compounds of the formula RR -CO-N / S, in particular, M, N-dimethylformamide, N, N-diethylformamide, N, N-dibutylformamide / N, N-dime. Ethyl acetate, M, M, K-diethylacetamide, N, N-ditsiklogeksylatsetamid, tiN-dimethylpropionamide, N, N-dietilpropionamid, N, N-ditsiklogeksilpropionamid, N, N-dietilg -P-butyramide, N, K-dymetilben3amid, N, N-ditsiklogeksilbenzamid, N, N -dietil- t-oluamide, N-acetylpyrrolidine, I-acetylpiperidine, Nn-butyrylpiperidine, 2-N-methylpyrrolidone, 2-M-ethylpyrrolidone, 2-Y-1-yutylpy (Veridone, K-ketilkaprodaktam, Essentially 2-K-methylpyrrolidone. The amount of solvent largely affects the rate of pea1iccIl and depends on the nature of the alcohol that is carbonylated and the solvent and on other reaction parameters. At least, the solvent content is not less than 20 vol. % of alcohol content. Thus, when acetic acid is obtained by carbonylation of methanol in the presence of N-methylpyrroidone, the amount of the latter is preferably at least 40% by volume of methanol. It is not necessary to purify or dry alcohol. Technical alcohols containing small amounts of water can be used. The carbonylation process according to the proposed method is carried out in the liquid phase under a pressure higher than atmospheric, a partial pressure of carbon monoxide below 150 atm, preferably 20-14.0 atm, Carbon monoxide is used in pure form, as an industrial product. However, in the presence of such impurities, such as carbon dioxide. oxygen, methane and nitrogen, as well as hydrogen, do not interfere with the process. At the end of the reaction, the reaction mixture is divided into various components by any method, for example, distillation. Example. A 250 ml autoclave with a capacity of 250 ml is charged with 27 ml of methanol, 70 ml of N-methyl pyrrolidone, 7.02 g (49 mmol) of distilled methyl, 12 g (72 mmol) of distilled potassium, and 20 mg at. nickel in the form of tetracarbonyl nickel (2.6 ml) sets a pressure of 45 atm using a mixture of CO - Hj in a ratio of 2: 1, then stirred using a system of reciprocating motion. The temperature in the autoclave is adjusted to approximately 20 minutes using a ring oven. The pressure in the autoclave reaches 60 atm and is maintained at this value by repeated loading of carbon monoxide. After 1 h, heating and stirring are stopped (complete absorption of carbon monoxide does not blunt at 64 atm). The autoclave is then cooled and degassed. After dilution, the resulting reaction mixture is analyzed by gas chromatography. 8.7 g of methyl acetate and 18.1 g of acetic acid are obtained. Acid production capacity is 250 g / hl. The yield of acetic acid is 45.3%. The output of methyl acetate 17.5%. Methanol conversion 80, 5%. PRI me R 2 (control). The process is carried out analogously to example 1, excluding potassium iodide. 2.9 g of methyl acetate and 1.2 g of acetic acid are obtained. Acid productivity 36 g / hl, Primerz (control). The process is carried out analogously to the example of It, eliminating methyl iodide and loading only 20 ml of methanol. Neither acetic acid nor methyl acetate is obtained. Examples 4-9. The process is carried out analogously to example 1, but different iodides of alkali or alkaline earth metals are used. The results are shown in Table. 1. PRI mmery 10 - 14. The process is carried out analogously to example 1, but load 70. ml of various solvents. The results are shown in Table. 2. Examples 15-19. A similar autoclave used in Example 1 was loaded with 27 ml of methanol, 70 MP of solvent, methyl iodide, 100 mmol of sodium iodide and 20 mg at. nickel in the form of tetracarbonyl nickel. A pressure of 45 atm is established with carbon monoxide, then the stirring system is switched on. The temperature in the autoclave is brought to 150 ° C for approximately 20 minutes. The pressure in the autoclave reaches 60 atm and is maintained at this value by repeated loads of carbon monoxide. - Duration of reaction 2h. The results are shown in Table. 3. Pr 180 g / hl in Example 15 and 165 g / hl in Example 16. Example 15: By analogy with Examples 15-19, an autoclave is charged with 20 mg atm. nickel in the form of Ni (CO),} 72 mmol KO, 43 mmol, 27 ml of ethanol and 70 ml of N-methylpyrrolidone. The initial pressure in the autoclave is 23 atm, the temperature is 150s. The total pressure is maintained at 40 atm by repeated loading of carbon monoxide. The reaction time is 5 hours. 6.3 t of propionic acid is obtained. PRI me R 21. Analogously to example 20, 10 mg at. nickel in the form of N1 (00) 4 mmol K 50 mmol CH3.3 g 27 ml of ben in silt alcohol and 70 ml of N-methylpyrrolidone. The reaction time is 4 hours. 24.2 g of phenylacetic acid are obtained. Example 22. A 250 ml autoclave with a capacity of 250 ml was charged with 20 ml of methanol, VO ml of N-methylshpolidone, 102 mmol of NaCC /. 35 mmol iodine and 32 mg-at. nickel in the form of N-t (OAc). A pressure of 45 atm is established using a mixture of CO - H2 in a 2: 1 ratio, and a stirring system is included. The temperature in the autoclave is adjusted to 180 ° C | for about 20 nbi. The pressure is maintained at a value of 60 atm by repeated loads of pure CO. The duration of the edition at the specified temperature is 2 hours. 3.6 g of methyl acetate and 20.2 g of acetic acid are obtained. Example 23: A 250 ml stainless steel autoclave is charged with 27 ml of methanol, 60 ml of M, H-dimethylCetamide, 43 mmol of NaBr, 125 mmol of p and 20 mg-at. nickel in the form of NI (€ 0) 4. A pressure of 40 atm is established with carbon monoxide and a stirring system is included. The temperature in the autoclave is adjusted to about 20 l / k. The pressure is maintained at a value of 60 atm by repeated loading of pure CO. The reaction time at the indicated temperature is 1 h 55 min. 6.8 g of methyl acetate and 19.6 g of acetic acid are obtained. (Ex 130 g / hl). Example 24 A 250 ml stainless steel autoclave is charged with 30 ml of methanol, 70 ml of α-methylphenrolidone, 100 mmol of NaD, 123 mmol and 4.2 g of nickel ene. The pressure is set to 45 atm with the aid of CO -.N mixture.
    in the 2: 1 ratio, the stirring system is turned on and the temperature in the autoclave is adjusted to within about 20 minutes. The pressure is maintained at a value of 60 atm by repeated loading of pure CO. The reaction time at the indicated temperature is 1 h 5 min. Obtain 1 g of methyl acetate and 28.2 g of acetic acid (Pr 270 g / hl).
    EXAMPLE 25 A stainless steel autoclave with a capacity of 250 ml was charged with 25 ml of methanol, 60 ml of N, N-dimethylacetamide, 66 mmol NaL, 200 mmol CjHyBr, and 19 mg-at. nickel in the form. The pressure is set to 45 atm using a mixture of CO - H in the ratio of 2: 1 and the stirring system is turned on. The temperature in the autoclave is adjusted to 16 5c b for about 20 minutes. The pressure is maintained at a value of 60 atm by loading loads of pure CO. The reaction time at the indicated temperature is 1 h 25 min. I get 7.5 g of methyl acetate and 15.2 g of acetic acid (Ex 150 g / CL.).
    PRI me R 26. A 250 ml stainless steel autoclave is charged with 27 ml of methanol, 70 ml of N-methylpyrrolidone, 72 mmol KO, 50 mmol and 20 mg-at. nickel in the form of N i (CO) 4. The pressure is set to 30 atm with carbon monoxide, the stirring system is turned on. The temperature in the autoclave is adjusted to within about 20 minutes. The pressure is maintained at a value of 40 atm by repeated loading of pure CO. The reaction time at the indicated temperature is 4 h 30 min. 2.5 g of methyl acetate and 41.2 g of acetic acid are obtained (Ex 96 g / hl).
    Example 27. A 250 ml autoclave with a capacity of 250 ml was charged with 47 ml of methanol, 50 mp of N-methylpyrrolidone, 72 mmol CZ,
    47 mmol and 20 mg at. nickel in the form of Ni (CO) 4. The pressure is set to 25 atm with carbon monoxide, the stirring system is turned on. The temperature in the autoclave was adjusted to about 20 minutes. The pressure was maintained at 40 atm by the second load of pure CO. The reaction time at the indicated temperature is 6 h 30 min, 14.4 g of methyl acetate and 39 g of acetic acid are obtained.
    Example 28. In a 250 ml autoclave with a capacity of 250 ml load 67 mp of methanol, 30 mp of N-methylpyrrolidone, 72 mmol CZ,
    48 mmol and 20 mg-at. nickel in the form of Ni (CO) 4 Set a pressure of 25 atm with carbon monoxide, include stirring. The temperature in the autoclave is adjusted to 150 ° C for approximately 20 minutes. The pressure is maintained at a value of 40 atm by repeated loads of pure CO. The reaction time at the indicated temperature is 4 hours. 10.7 g of methyl acetate and 4.2 g of acetic acid are obtained.
    PRI me R 29. In the autoclave of
    0 250 ml stainless steel was charged with 20 ml of methanol, 70 ml of N-methylpyrrolidone, 72 mmol KD, 164 mmol and 20 mg-at. nickel in the form of N (CO) 4. A pressure of 45 atm is established using a mixture of CO - H2 in a 2: 1 ratio, including the stirring system. The temperature in the autoclave is adjusted to within about 20 minutes. The pressure is maintained at a value of 60 atm by repeated loading of pure CO. -Duration of the reaction at the specified temperature for 2 hours. 8.0 g of methyl acetate are obtained to 29 g of acetic acid (Ex 180 g / hl).
    ExampleROS. Into a 250 ml autoclave with a capacity of 250 ml, 29.5 ml of methanol, 7T) ml of N-methylpyrrolidone, 72 mmol CZ, 10 mmol and 20 mg-at. nickel in
     form. N i (WITH) c. The pressure is set to 45 atm with the AID of a mixture of CO - Hj in the ratio of 2: 1, and the stirring system is turned on. The temperature in the autoclave is adjusted to 150 ° C for
    5 approximately 20 min. The pressure is maintained at a value of 60 atm by repeated loading of pure CO. Duration of the reaction at the indicated temperature is 1 h. 2.65 g are obtained.
    0 methyl acetate and 0.18 g of acetic acid.
    PRI m im 31. In a 250 ml stainless steel autoclave with a capacity of 250 ml load 27 ml. methanol, 70 ml
    5 N-methylpyrrolidone, 100 mmol KO, 50 mmol and 20 mg-at. nickel in the form of NI (CO) 4. A pressure of 45 atm is established using a mixture of CO Nl in a ratio of 2: 1, including ne „stirring. The temperature in the autoclave was adjusted to .21. for about 20 min. The pressure is maintained at a value of 60 atm by repeated loading of pure CO. The reaction time at the indicated temperature is 1 hour. 0.98 g of methyl acetate and 36.5 g of acetic acid are obtained (PR 375 g / hl).
    Example 32. A 250 ml stainless steel autoclave with a capacity of 250 ml
    0 load 27 ml of methanol, 70 ml of N-methylpyrrolidone, 72 mmol CZ, 49 mmol and 5 mg-at. nickel in the form of NiCCO). A pressure of 22 atm is established with the help of oxide
    5 carbon include stirring system. The temperature in the autoclave is brought to within about 20 minutes. The pressure is maintained at a value of 40 atm by repeated loading of pure CO. The duration of the reaction at. the indicated temperature is 5 hours. 7.7 g of methyl acetate and 14.7 g of acetic acid are obtained.
    Example 33. A 250 ml stainless steel autoclave was charged with 27 ml of methanol, 70 ml of N-methylpyrrolidone, 51 mmol of CHOO, 100 mmolKZ and 20 mg-at, nickel in the form of N4 (00) 4. The pressure was set at 45 atm using a mixture of CO H in the ratio of 2: 1, and the stirring system was turned on. The temperature in the autoclave is adjusted to within about 20 minutes. The pressure is maintained at a value of 60 a by repeated loads of pure CO. Duration of the reaction at the indicated temperature is 1 h. 5.8 g of methiladetate and 31.3 g of acetic acid (P 360 g / hl) are obtained. PRI me R 34. A 250-ml stainless steel autoclave was charged with 27 mp of methanol, 70 ml of N-methylpyrrolidone, 40 mmol, 72 mmol cp, and 10 mg-at. Nickel in the form of Ni (CO) ij. The pressure is set to 25 atm with carbon monoxide. The system is turned on. The temperature in the autoclave is adjusted to within about 20 minutes. The pressure is maintained at a value of 4-0 atm by repeated loading of pure CO. The reaction time at the indicated temperature is 5 hours. 4.5 g of methyl acetate and 37.2 g of acetic acid are obtained.
    EXAMPLE 35 A stainless steel autoclave with a capacity of 250 ml is charged with 27 ml of methanol, 70 ml of N-methylpyrrolidone, 49 mmol, 100 mmol kZ and 20 mg-at. nickel in the form of Ni (CO) 4. A pressure of 45 atm is established using a mixture of CO H in a 2: 1 ratio, and a stirring system is included. The temperature in the autoclave is adjusted to 150 s for approximately 20 minutes. The pressure is maintained at 60 atm by repeated loads of pure CO. Duration of the reaction at the indicated temperature is 1 h. 8.5 g of methyl acetate and 22.7 g of acetic acid are obtained (Ex 295 g / hl). PRI m, er 36. In the autoclave. 250 ml stainless steel was charged with 27 ml of methanol, 70 ml of N-methylpyrrolidone, 20 mmol K3f 51 mmol and 20 mg-at. nickel in the form of Ni (CO) (. The pressure is set to 45 atm using a mixture of CO RP in the ratio 2: 1, the stirring system is turned on. The temperature in the autoclave is adjusted to approximately 20 minutes. The pressure is maintained at 60 atm by repeated loading pure CO. The duration of the reaction at the indicated temperature is 1 hour. 7 g of methyl acetate and 5.5 g of acetic acid are obtained (Pr 110 g / h).
    Example 37. A 250 ml stainless steel autoclave is charged with 27 ml of methanol, 70 ml of N-methylpyrrolidone, 49 mmol f 150 mmol KO and 20 mg-at. nickel in the form of Nt (CO) 4. The pressure is set to 45 atm. using a mixture of CO - H in the ratio of 2: 1, include a mixing system. The temperature in the autoclave is adjusted to within about 20 minutes. The pressure is maintained at a value of 60 atm by repeated loading of pure CO. The reaction time at the specified temperature is 1 h. 8.8 g of methyl acetate and 25.4 g of acetic acid (Pr 215 g / hl) are obtained.
    PRI me R ZV. A stainless steel autoclave with a capacity of 250 ml was charged with 28.5 ml of methanol, 70 ml of N-methylpyrrolidone, 28 mmol, 72 mmol of short-circuit and 20 mg-at. nickel in the form of NI (co) 4i. The pressure is set to 45 atm using a mixture of CO Hi 2 in a ratio of 2: 1 and the stirring system is turned on. The temperature in the autoclave is adjusted to within about 20 ms. The pressure is maintained at a value of 60 atm by repeated loading of pure CO. The reaction time at the specified temperature is 1 h. 9.95 g of methyl acetate and 3.4 g of acetic acid are obtained (PR 110 g / hl).
    PRI meper 39. In a 250 ml stainless steel autoclave. load 27 ml of methanol, 70 ml of N-methylpyrrolidone t 100 mmol CZ, 50 mmol and 20 mg-at. nickel in the form of Ni (CO) 4. A pressure of 45 atm is stopped at a mixture of CO - KH in a ratio of 2: 1, and a stirring system is included. The temperature in the autoclave is adjusted to 150 ° C in approximately 20 minutes. The pressure is maintained at a value of 60 atm for in-stream loading of pure CO. Duration of reaction at the indicated temperature; 1 hour. 8.3 g of methyl acetate and 20.2 g of acetic acid are obtained (PR 270 g / Chl).
    Example 40. A 250 ml autoclave with a capacity of 250 ml is charged with 27 ml of methanol, 70 ml of N-methylpyrrolidone, 45 mmol, 40 mmol K: 31 and 20 mg-at. nickel in the form of N.i (CC)) 4. A pressure of 45 atm is established using a mixture of CO - H2 in a ratio of 2: 1, including a mixing system. The temperature in the autoclave is adjusted to within about 20 minutes. The pressure is maintained at a value of 60 atm with repeated loads of pure CO. The duration of the reaction at the indicated temperature is 1 hour. 8.15 g of methyl acetate and 9.9 g of acetic acid are obtained (Pr 165 g / h-l). EXAMPLE 41 E stainless steel autoclave with a capacity of 250 ml is charged with 25 ml of methanol, 70 ml of N-, methylpyrrolidone, 72 mmol of short-circuit, 81 coyle of CHD and 20 mg-at, nickel in the form) 4 Set pressure is 45 atm using a mixture of CO - H in the ratio of 2: 1, include a mixing system. The temperature in the autoclave is adjusted to 150 for approximately 20 minutes. The pressure is maintained at a value of 60 atm by repeated loading of pure CO. The reaction time at the indicated temperature is 1 h. Obtain 8.1 g of methyl acetate and 19.9 g of acetic acid (Ex 265 g / h-l). For example, 23 ml of methanol, 64 ml of y-methylpyrrolidone, 73 mmol of Na3, 49 mmol and 20 mg atm are charged into a 225 ml tantalum autoclave. nickel in the form of Ni (CO). A pressure of 23 atm is established with the aid of carbon monoxide, a stirring system is included. The temperature in the autoclave was adjusted to about 20 minutes. The pressure is maintained at a value of 40 atm by repeated loading of pure CO. The reaction time at the specified temperature is 1 h. Get Methyl acetate Acetic acid ixni; yi; "ein lima. Performance of acetic acid, the reaction volume MD 32 8 HjO 10 g of methyl acetate and 11.3 g of acetic acid (Pr 200 g / CL). Example43. In autoclave with stainless steel tank. 250 ml were charged with 28 ml of methanol, 64 ml of N-butylpyrrolidone, 49 mmol, 73 mmol of NaAZ, and 20 mg-at. nickel in the form of (CO} 4. The pressure is set to 23 atm with carbon monoxide, the stirring system is turned on. The temperature in the autoclave is adjusted to about 20 minutes. The pressure is maintained at 40 atm by repeated cooling 4 and pure CO. Duration of the reaction at the specified temperature 1 h. Obtain 8.2 g of methyl acetate and 16.1 g of acetic acid (PR 220 g / day). PRI me R s 44 - 47. A 250 MP stainless autoclave with a capacity of 250 MP is charged with 50 to mol, 72 mmol. CZ, 27 ml of methanol, 70 mp of N-methylpyrrolidone and 20 mg-at. Nickel in the form S (CO} c. The reaction is carried out at The carbon monoxide partial pressure (at the reaction temperature) and the results are shown in Table 4. Based on the data given in Table 4, the graphical dependence of the influence of carbon monoxide partial pressure (p) deposited on the abscissa and expressed in atmospheres on the reaction rate tv), plotted on the ordinate and expressed in moles of carbon monoxide absorbed in 1 hour of the reaction (see drawing). Table. received for 1 h and 1 l
    Tetramethylenesulfone
    Tetramethyl urea
    Tetraglim
    Dimethylformamide Dimethylacetamide. The experiment was carried out with 100 mmol of KO in
    Table 2
    4.2
    10.5
    8.2 for 3 h 45 min. Table 3
    权利要求:
    Claims (3)
    [1]
    1. METHOD FOR PRODUCING MONOCARBOXYLIC ACIDS of general formula (1). R-COOH where R is methyl, ethyl or benzyl, by liquid-phase carbonylation of an alcohol of the general formula (I)
    R-OH
    V where R has the indicated values, at 150-2 ° C, a partial pressure of carbon monoxide of 20-140 atm using a nickel-containing catalyst in an amount of 50-320 mg-at. nickel on. 1 l of the reaction mixture in the presence of haloalkyl, with the exception that, in order to simplify and increase productivity, the process is carried out in the presence of an alkali or alkaline earth metal halide in a solvent medium selected from the group consisting of tetramethylene sulfone , tetraglyme, Ν, Ν-di- (alkyl C ^ -C 4 ) -acetamide, Ν, Ν-dibutylformamide, Ν, Ν-diethyltoluamide, Ν- (alkyl C <- C4) - §
    -pyrrolidone, N-methylpiperidone, with a volume ratio of alcohol to solvent equal to 1: 0.4-4, with a ratio of haloalkyl to nickel equal to 1 mole / g-at. and an alkali or alkaline earth metal halide to nickel equal to 1 mole / g-at.
    SU „„ 102
    [2]
    2. The method according to π. 1, characterized in that iodine alkyl C (—C 4 .
    [3]
    3. The method according to π. 1, due to the fact that iodide is used as an alkali or alkaline earth metal halide.
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    同族专利:
    公开号 | 公开日
    JPS582215B2|1983-01-14|
    JPS55145634A|1980-11-13|
    ES490853A0|1980-12-01|
    DE3060208D1|1982-03-25|
    DD150196A5|1981-08-19|
    ES8100656A1|1980-12-01|
    BR8002443A|1980-12-02|
    FR2455021A1|1980-11-21|
    EP0018927B1|1982-02-24|
    EP0018927A1|1980-11-12|
    CA1149413A|1983-07-05|
    AT719T|1982-03-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS4731283U|1971-04-27|1972-12-08|
    JPS5441174B2|1973-07-16|1979-12-07|
    JPS6056692B2|1977-09-29|1985-12-11|Mitsubishi Gas Chemical Co|
    JPS562057B2|1977-11-01|1981-01-17|FR2489817B1|1980-09-11|1983-10-21|Rhone Poulenc Ind|
    FR2491919B1|1980-10-09|1984-01-13|Rhone Poulenc Chim Base|
    FR2496645B1|1980-12-24|1984-02-10|Rhone Poulenc Chim Base|
    EP0124160B1|1983-05-02|1986-09-17|Shell Internationale Researchmaatschappij B.V.|A process for the preparation of carboxylic acids and/or esters|
    GB8320358D0|1983-07-28|1983-09-01|Shell Int Research|Preparation of carboxylic acids|
    CA1237728A|1984-07-20|1988-06-07|Anthony G. Abatjoglou|Production of carboxylic acids from alcohols usingrhodium complex catalysts|
    US5026907A|1984-08-16|1991-06-25|Union Carbide Chemicals And Plastics Technology Corporation|Production of carboxylic acids from alcohols using rhodium complex catalysts and organic ester source|
    JPH072670B2|1988-07-26|1995-01-18|カウンスル・オブ・サイエンティフィク・アンド・インダストリアル・リサーチ|Method for producing carboxylic acid|
    US5218140A|1988-08-02|1993-06-08|Union Carbide Chemicals & Plastics Technology Corporation|Carbonylation reaction and catalyst therefor|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7911209A|FR2455021A1|1979-04-25|1979-04-25|PROCESS FOR THE PREPARATION OF CARBOXYLIC ACIDS BY CARBONYLATION|
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