• 专利附录
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  • 权利要求
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    • 专利摘要:

    公开号:SU1834883A3
    申请号:SU915001696
    申请日:1991-10-02
    公开日:1993-08-15
    发明作者:Dzhordzh Biver Robert；Angus Griner Nejl；Dzheffri Gulliver Devid；Mikael Sorrell Robert
    申请人:Bp Kemikalz Limited；
    IPC主号:
    专利说明:

    UNION OF SOVIET
    SOCIALIST
    REPUBLIC
    1834883 AZ (505 С 07 С 51/10, 51/09 _____
    STATE PATENT
    DEPARTMENT OF THE USSR (GOSPATENT USSR)
    DESCRIPTION OF THE INVENTION
    TO THE PATENT
    (21) 5001696/04 (22) 02.10.91 (31) 9021454.5 (32) 03.10.90 (33) GB (46) 08/15/93. Bull. No. 30 (71) BP Chemicals Limited (G8) (72) Robert George Beaver, Neil Angus Griner, David Jeffrey Gulliver and Robert Michael Sorrell (GB) (56) British Patent No. 1538783, cl. With 2 S. publ. 1979.
    U.S. Patent No. 4,430,273, cl. C 07 C 51/12, published. 1984.
    EP No. 153834, class C 07 C 53/08, published. 1985.
    EP No. 391680, class C07 C51 / 12, published 1990.
    EP No. 87870, ’cl. C 07 C 51/56, published 1983.
    This invention relates to a carbonylation process, and in particular to a liquid phase carbonylation process in the presence of rhodium catalysts in order to produce carboxylic acid anhydrides.
    The technical problem to be solved with the help of this invention was to develop a co-promoter for rhodium-catalyzed liquid-phase carbonylation processes to produce carboxylic acid anhydrides under practically anhydrous conditions, (54) METHOD FOR PRODUCING ACETIC ANHYDRIDE (57) SUMMARY OF THE INVENTION: Acetic product the anhydride is obtained by reacting methyl acetate with carbon monoxide under anhydrous conditions at a pressure of 10-100 bar, a temperature of 100-250 ° C in the presence of a rhodium catalyst added to the col 10-2000 ppm, with an iodide promoter with a concentration providing a molar ratio of rhodium to iodide from 1:10 de 1: 1000, and with a co-promoter - 1,3,4-trimethylimidazolium iodide or 1,2,3,4,5- pentamethylimidazolium iodine in an amount providing a molar ratio to rhodium catalyst from 0.5: 1 to 10: 1. In this case, the co-promoter can be obtained by quaternization of the corresponding imidazole with an alkyl iodide, and imidazole - by alkylation of a less substituted imidazole with an alkyl iodide. Characteristic: increased stability. 2 wpp, 2 tab.
    which would reduce the tendency to precipitate and / or instability of the rhodium catalyst.
    Thus, according to this invention, a method for producing carboxylic acid anhydrides has been developed, which comprises reacting in the reaction zone, under practically anhydrous conditions of carbon monoxide, with a carboxylic acid ester or an alkyl ether in the presence of a rhodium catalyst. iodide as a promoter and co-promoter, characterized in that the co-promoter is selected from the group consisting of 1,834,883 AZ 1,3,4-trimethidimidazolium iodide and
    1,2,3,4,5-pentamethylimidazolium iodide.
    This invention solves the above problem by using some selected quaternary ammonium iodides, which, as shown, do not form appreciably soluble rhodium-containing complexes, even under harsh conditions that contribute to the instability of the rhodium catalyst.
    Under practically anhydrous conditions in the reaction zone is meant a complete absence of water or a water concentration of less than 0.1% by weight.
    The method may be carried out in a batch or continuous manner, preferably continuous. In a continuous process, the reaction medium can be continuously withdrawn from the reaction zone and carboxylic acid anhydride is isolated from it before the catalyst and promoters are recycled to the reaction water. It is in the process of such separation of the catalyst and promoter from the reaction medium that precipitation of the rhodium catalyst can occur, for example, due to a lack of '; carbon monoxide compared to its amount in the reaction zone. It is believed that the co-promoter of the invention can provide improved solubility and stability of the rhodium catalyst during such separation and thereby increase the productivity and / or progress of the reaction under more favorable conditions.
    The carboxylic acid ester and alkyl ether preferably contain from 2 to 6 carbon atoms. Preferred reactants are methyl acetate, ethyl acetate and dimethyl ether. ^ A controlled amount of alkanol, for example methanol or ethanol, and / or water, which forms with a carboxylic acid ester and / or an alkyl ether introduced into the reaction zone, carboxylic acid, provided that practically anhydrous conditions are maintained in the reaction zone. For example, a controlled amount of methanol and / or water can be introduced into the reaction zone with methyl acetate to produce acetic acid in addition to acetic anhydride, provided that practically anhydrous conditions are preserved in the reaction aeon.
    Any soluble rhodium-containing catalyst used in the carbonylation of esters or ethers can be used here. The source of rhodium can be, for example, a simple inorganic salt, such as rhodium chloride, bromide, iodide or rhodium nitrate, a carbonyl or organometallic complex of rhodium, or a coordination complex. You can also use finely ground metallic rhodium, which dissolves in the reaction medium.
    The iodide as a promoter used in combination with the catalyst can be added as elemental iodine, hydrogen iodide, iodide salt, for example sodium iodide, or an organic source of iodine, such as alkyl or aryl iodide. A preferred source of iodine component is methyl iodide. Perhaps part of the iodide along with rhodium, for example, when using a compound such as rhodium triiodide. The concentration of iodide is such that the molar ratio of rhodium to iodide is at least 1: 4, preferably from 1:10 to 1: 1000. ·
    The co-promoter is present in such quantities that the molar ratio of the co-promoter to the rhodium catalyst is not more than 0.5: 2, preferably from 0.5: 1 to 10 J : 1. The co-promoter of the present invention can be prepared separately, before it is introduced into the reaction zone, or it can be obtained in situ, for example, by quaternization of the corresponding imidazole with an in situ alkyl iodide source. Imidazole itself can be obtained in situ by alkylating a less substituted imidazole with a source of alkyl iodide, such as methyl iodide.
    The carbonylation reaction described herein is carried out in a liquid phase consisting of a solution of a catalyst system. In general, the concentration of the soluble rhodium component will be such that it ranges from 10 ppm to 20,000 ppm, preferably from 10 ppm to 10,000 ppm, and most preferably from 10 ppm to 3,000 ppm of the reaction mixtures.
    The process is carried out at elevated pressure and elevated temperature. Although the optimal conditions will be determined by the specific type of feedstock and catalyst system used, nevertheless, the reaction is usually carried out at a pressure of more than 10 bar, preferably from 10 to 100 bar, and a temperature lying in the range from 100 to 250 ° C. For the preferred types of feed indicated here, the optimal ranges of temperature and pressure will vary somewhat. However, the specific limits of such optimum temperatures and pressures for this type of feed are known to those skilled in the art of carbonylation.
    Preferably, the carbon monoxide used in the practice of this invention is as clean as possible. However, often the process of producing carbon monoxide is accompanied by the formation of a certain amount of diluent gases, such as nitrogen and hydrogen, which may be present in the reaction zone. If hydrogen is present, then its amount should correspond to the permissible level of by-products formed from it. It is preferable that the partial pressure of hydrogen in the reaction zone is from 0.01 to 10 bar, more preferably from 0.1 to 3 bar.
    A known method of producing acetic anhydride, accompanied or not accompanied by the simultaneous formation of acetic acid from methanol and carbon monoxide in successive stages of esterification, carbonylation and separation, including (1) the interaction of methanol with recycle acetic acid in the stage of esterification with the formation of an esterification product containing mainly methyl acetate , water and optionally reacted methanol, (2) removing part of the water from the esterification product, (3) product interaction esterification, still containing water, with carbon monoxide in the carbonylation step in the presence of free or bound halogen as a catalyst to form a carbonylation product containing acetic acid and acetic anhydride, (4) separation of carbonylation products by fractional distillation into a low boiling fraction containing the starting compounds for carbonylation and volatile components of the carbonylation promoter, acetic acid and acetic anhydride and a higher boiling fraction containing carbonylation catalyst components, (5) recycling a low boiling fraction containing carbonylation starting compounds and components of a carbonylation promoter, and a higher boiling fraction containing carbonylating catalyst components, to a carbonylation step, and (6) recycling at least a portion of acetic acid to a step esterification.
    The following examples illustrate the solubilizing and stabilizing effect of the co-promoters of this invention.
    Preparation of the mother liquor of the rhodium catalyst.
    In a 300 ml Hadtellog B2 autoclave, a mixture of rhodium triiodide (6.28 g, 13.00 5 mmol), water (28.0 g) H1 (4.0 g 57% aqueous solution) and glacial acetic acid (134, 0 g). The autoclave was hermetically sealed and charged with carbon monoxide in an amount of 30 barg, heated to 180 and C and 10 were maintained at this temperature for 48 hours. At the end of this period, the autoclave was cooled and purged. The solution was centrifuged and analyzed for the rhodium content by acid absorption followed by atomic absorption spectroscopy. Typically, the mother liquor of the catalyst contains from 2000 to 3000 ppm of rhodium. Before use, the mother liquor was filtered.
    Preparation of quaternized imidazoles.
    Quaternized imidazoles according to this invention and as such 25 are generally obtained by treating the corresponding imidazole in tetrahydrofuran with 3-4 equivalents of methyl iodide, followed by boiling for 12 hours. In some cases, under the action of methyl iodide, im30, the dazole is alkylated and quaternized. Quaternized imidazoles and the corresponding imidazoles are discussed below. Products isolated from these reaction mixtures were further treated with methyl iodide in a mixture of acetic acid, acetic anhydride and methyl acetate at a temperature of 180 ° C in a Fischer-Porter tube in the first stage of the solubility test (stability with 40 to ensure complete quaternization of imidazole).
    Examples of the Invention
    Quaternized Imidazole Imidazole
    1,3,4-trimethylimidazolium iodide 4-methylimidazole 1.2.3,4,5-pentamethylimidazo-1,2-dimethylimilium iodide dazole
    Example 1. 3.62 g of 1,3,4-trimethylimidazolium iodide prepared as described above was added to a solution of acetic anhydride (3.33 g), methyl acetate (2.33 g), methimodide (2; 85 g) and acetic acid ( 5.11 g). Then 55 the mixture was heated in a Fischer-Porter tube for 12 hours at 180 ° C under a nitrogen pressure of 1 bar. At the end of this period, the solution was cooled to room temperature and 2.95 g of the mother liquor ___ catalyst was added. The solution was stirred for 1 h at room temperature, and then a sample was taken from it. The sample solution was centrifuged and the solution was analyzed for rhodium by acid absorption followed by atomic absorption spectroscopy in order to obtain a measure of the solubility of the rhodium catalyst in the presence of a co-promoter.
    The remaining solution was heated at 180 ° C under a nitrogen pressure of 1 bar for 22 hours. At the end of this period, the solution was cooled and a sample was taken from it. The sample solution was centrifuged and the solution was analyzed for rhodium by acid absorption followed by atomic absorption spectroscopy in order to obtain a measure of the stability of the rhodium catalyst in the presence of a co-promoter. The results are presented in table 1.
    For example, 2.3.59 g of 1,2,3,4,5-pentamethylimidazolium iodide prepared as described above was added to a solution of acetic anhydride (3.31 g), methyl acetate (2.38 g), methidiodide (2.67 g) and acetic acid (5.12 g). The mixture was then heated in a Fischer-Porter tube for 12 hours at 180 ° C. under a nitrogen pressure of 1 bar. At the end of this period, the solution was cooled to room temperature and 3.00 g of the mother liquor of the catalyst was added. The solution was stirred for 1 h at room temperature, and then a sample was taken from it. The sample solution was centrifuged and the solution was analyzed for rhodium by acid absorption followed by atomic absorption spectroscopy in order to obtain a measure of the solubility of rhodium in the presence of a co-promoter.
    The remaining solution was heated at 180 ° C under a nitrogen pressure of 1 bar for 22 hours. At the end of this period, the solution was cooled and a sample was taken from it. The sample solution was centrifuged and the solution was analyzed for rhodium by acid absorption followed by atomic absorption spectroscopy in order to obtain a measure of the stability of the rhodium catalyst in the presence of a co-promoter.
    The results are presented in table 1. ''
    Comparative Experiments Comparative Experiment A 3.61 g of 1,2,3-trimethylimidazolium iodide prepared as described above was added to a solution of acetic anhydride (3.31 g), methyl acetate (2.38 g), methyl iodide (2.86 g) Acetic acid (5.11 g) The mixture was then heated in a Fischer-Porter tube for 12 h at 180 ° С under a nitrogen pressure of 1 bar. At the end of this period, the solution was cooled to room temperature and 3.00 g of the mother liquor of the catalyst was added. The solution was stirred for 1 h at room temperature, and then a sample was taken from it. The sample solution was centrifuged and the solution was analyzed for rhodium by acid absorption, followed by atomic absorption spectroscopy in order to obtain a measure of the solubility of the rhodium catalyst in the presence of a co-promoter.
    The remaining solution was heated at 180 ° C and 1 bar nitrogen pressure for 22 hours. At the end of this period, the solution was cooled and a sample was taken from it. The sample solution was centrifuged and the solution was analyzed for rhodium by acid absorption, followed by atomic absorption spectroscopy in order to obtain a measure of the stability of the rhodium catalyst in the presence of a co-promoter. The results are presented in table 1.
    Comparative Experiment B
    3.65 g of 1,3-dimethylimidazolium iodide prepared as described above was added to a solution of acetic anhydride (3.30 g), methyl acetate (2.40 g), methyl iodide (2.89 g) and acetic acid (5.13 d). The mixture was then heated in a Fischer-Porter tube for 12 hours at 180 ° C under a nitrogen pressure of 1 bar. At the end of this period, the solution was cooled to room temperature and 2.89 g of the mother liquor of the catalyst was added. The solution was stirred for 1 h at room temperature, and then a sample was taken from it. The sample solution was centrifuged and the solution was analyzed for Rhodium content by acid absorption followed by atomic adsorption spectroscopy in order to obtain a measure of the solubility of the rhodium catalyst in the presence of a co-promoter.
    The remaining solution was heated at 180 ° C and 1 bar nitrogen pressure for 22 hours. At the end of this period, the solution was cooled and a sample was taken from it. The sample solution was centrifuged and the solution was analyzed for rhodium by acid absorption followed by atomic absorption spectroscopy in order to obtain a measure of the stability of the rhodium catalyst in the presence of a co-promoter. The results are presented in table 1.
    Examples 4 and 5 and Comparative experiments C and D.
    Further experiments were performed using increased amounts of acetic anhydride.
    Preparation of quaternized imidazoles.
    Quaternized imidazoles were obtained by treating the corresponding free base in dichloromethane with 3-4 equivalents of methyl iodide, followed by boiling for 3 hours. The target product was isolated after removal of the solvent in vacuo.
    Comparative experiment C.
    The 1,3-dimethylimidazolium iodide (2.789 g) obtained as described above was added to a solution of acetic anhydride (4.205 g), acetic acid (11.511 g), methyl iodide (3.111 g) and methyl acetate (3.001 g).
    The mixture was then heated in a Fischer-Porter vessel for 21 hours at 180 ° C. under a nitrogen pressure of 1 bar. At the end of this period, the solution was cooled to room temperature and [Rh / CO / 2Clh 0.0305 g was added. The solution was stirred for 1 h at room temperature and a sample was taken from it. The sample solution was centrifuged and the solution was analyzed for rhodium by acid absorption, followed by atomic absorption spectroscopy in order to obtain a measure of the solubility of the rhodium catalyst in the presence of a co-promoter.
    The remaining solution was heated at 180 ° C and 1 bar nitrogen pressure for 12 hours. At the end of this period, the solution was cooled and a sample was taken from it. The sample solution was centrifuged and the solution was analyzed for rhodium by acid absorption followed by atomic absorption spectroscopy in order to obtain a measure of the stability of the rhodium catalyst 8 in the presence of a co-promoter. The results obtained are presented in table.2.
    Example 4. 1,3.4-Trimethylimidazolium iodide (2,368 g), prepared as described above, was added to a solution of acetic anhydride (4.223 g), acetic acid (10.629 g), methyl iodide (3.223 g) and methyl acetate (3.2 Yu g) . The mixture was then heated in a Fischer-Porter vessel for 12 hours at 180 ° C. under a nitrogen pressure of 1 bar. At the end of this period, the solution was cooled to room temperature and [Rh / CO / ji Clh (0.0298 g) was added. The solution was stirred for 1 h at room temperature, and then a sample was taken from it. The sample solution was centrifuged and the solution was analyzed for mercury content by acid absorption, followed by atomic adsorption spectroscopy in order to obtain a measure of the solubility of the rhodium catalyst in the presence of a copro motor.
    The remaining solution was heated at 180 ° C and 1 bar nitrogen pressure for 12 hours. At the end of this period, the solution was cooled and a sample was taken from it. 10 The sample solution was centrifuged and the solution was analyzed for rhodium content by acid absorption followed by atomic adsorption spectroscopy in order to obtain a measure of the stability of the rhodium catalyst in the presence of a co-promoter. The results obtained are presented in table.2.
    Example 5. 1,2,3,4,5-Pentamethylimidazolium iodide (2.444 g), prepared as described above, was added to a solution of acetic anhydride (4.215 g), acetic acid (10.991 g), methyl iodide (3.330 g), and methyl acetate (3.006 g). The mixture was then heated in a Fischer-Porter vessel for 12 hours at 25-180 ° C and a nitrogen pressure of 1 bar. At the end of this period, the solution was cooled to room temperature and [Rh / CO / 2CI] 2 (0.0337 g) was added. The solution was stirred for 1 h at room temperature, and then 30 samples were taken from it. The sample solution was centrifuged and the solution was analyzed for rhodium content by acid absorption followed by atomic absorption spectroscopy in order to obtain a 35 measure of the solubility of the rhodium catalyst in the presence of a co-promoter.
    The remaining solution was heated at 180 ° C and a nitrogen pressure of 1 bar for 12 hours. At the end of this period, solution 40 was cooled and a sample was taken from it. The sample solution was centrifuged and the solution was analyzed for rhodium content by acid absorption followed by atomic adsorption spectroscopy in order to obtain a measure of the stability of the rhodium catalyst in the presence of a co-promoter. The results obtained are presented in table.2.
    Tab results show that under harsh conditions, the co-promoters of this invention provide a higher concentration of rhodium in solution than other co-promoters.
    'Experiments on the carbonylation reaction55.
    Preparation of Quaternized ’Imidazole - Experiment 6.
    1,2,4,5-tetramethylimidazole was treated with 3-4 molar equivalents of methidiodide in dichloromethane as a solvent and boiled for 3 hours. Then the solvent was removed in vacuo to give 1,2.3,4.5-pentamethylimidazolium iodide. which was used in the subsequent carbonylation reaction.
    The carbonylation reaction in the presence of 1,2,3,4,5-pentamethylimidazolium iodide - Experiment 7.
    In 100 ml of a Hastallog autoclave, 2, 1.2.3,4,5-pentamethylimidazolium iodide (9.02 g) was prepared, obtained as described above, acetic anhydride (5.21 g), methyl acetate (6.81 g), methyl iodide (7 , 96 g), acetic acid (21.01 g) and (Rh / CO / 2CI] 2 (0.072 g) is equivalent to 761 ppm of rhodium in the contents of the reactor. The autoclave was tightly closed and its pressure increased to 4 bar by feeding carbon monoxide and heated to 180 ° C. Upon reaching a stable temperature, the pressure was increased to 41 bar due to the further supply of carbon monoxide.The temperature was maintained for 1 h, during which carbon monoxide absorption was measured by pressure drop. At the end of this period, the autoclave was cooled and its pressure was reduced, and the contents were subjected to gas chromatographic analysis. The yield of acetic anhydride was 3.31 g, which corresponds to 35.2% methyl acetate conversion. the absorption of carbon monoxide was 3.35 mol / kg / h.
    权利要求:
    Claims (3)
    [1]
    1. The method of producing acetic anhydride by the reaction of methyl acetate with carbon monoxide under anhydrous conditions at a pressure of 10-100 bar, at a temperature of 100-250 ° C in the presence of a rhodium catalyst component of 10-2000 ppm, an iodide promoter with a concentration providing the molar ratio of rhodium to iodide 1: 10-1: 1000, and the co-promoter in an amount providing a molar ratio of co-promoter to rhodium catalyst of 0.5: 1-10 5 : 1, characterized in that a substance selected from the group consisting of 1,3,4-trimethylim dazoliyiodida and 1,2,3,4,5-pontametilimidazoliyiodida.
    [2]
    2. The method according to claim 1, characterized in that they use a co-promoter obtained * in situ by quaternization of the corresponding imidazole with adqiliodide.
    [3]
    3. The method according to claim 2, characterized in that the corresponding imidazole is obtained in situ by alkylation of a less substituted imidazole with an alkyl iodide.
    Table 1
    Experiment Rhodium solubility (ppm) Rhodium stability (parts per million) 1 317 324 2 298 308 ComparativeA 40 42 Comparativein 36 70
    Note. The results in the table are adjusted for small inevitable losses of volatile components during the experiments.
    table 2
    Example Rhodium solubility (ppm) Rhodium stability (parts per million) Comparative Experiment D 35 66 4 235 877 5 335 813
    Note. The results are corrected for small inevitable losses of volatile components during the experiments. Concentrations characterizing stability are higher than those characterizing solubility due to increased dissolution upon heating.
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