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    • 专利摘要:
    Method for the hydroformylation of olefins with carbon monoxide and hydrogen in the presence of soluble cobalt compounds as the catalyst at an elevated temperature and under increased pressure, and optionally in the presence of paraffins and/or other inert diluents. The hydroformylation is conducted, in a first stage, up to a conversion of about 40-75 percent with remixing of the reaction mixture, and then, in a second stage, up to a conversion of at least 95 percent, preferably 95-98 percent, without remixing.
    公开号:SU847911A3
    申请号:SU762389508
    申请日:1976-08-23
    公开日:1981-07-15
    发明作者:Кауфгольд Манфред；Гаубе Иоганн
    申请人:Хемише Верке Хюльс Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to organic chemistry, specifically to an improved method for producing alcohols, which can be used as intermediates in the manufacture of various chemical compounds. A known method of producing alcohol by hydroformylation of olefins with more than 6 carbon atoms in the presence of a soluble cobalt catalyst at 100-250 seconds and 70500 atm. The yield of alcohols is 50% when the degree of conversion of olefinic B is 85% 1. However, the method is not characterized by a sufficiently high yield of the target product and not by the complete conversion of the starting olefins. The purpose of the invention is to increase the yield of the target product. The goal is achieved by the fact that the process of hydroformylation of olefins is carried out in two stages, and in the first stage to achieve the degree of conversion of olefins 40-75% in a continuous-action reactor with vigorous stirring of the initial olefins with the reaction mixture 95-98% in the second reactor of tubular type. The method of producing alcohols is that the mixture of straight-chained and / or branched olefins containing 6-20 carbon atoms is reacted with carbon monoxide and hydrogen in the presence of a soluble cobalt catalyst at 130-200 ° C and 200-350 atm, while the process carried out in two stages: in the first stage, to achieve the degree of conversion of the olefinor of 40-75% in a continuous reactor with vigorous stirring of the initial olefins with the reaction mixture, and in the ethereal stage to achieve the degree of conversion of 95-98% in the second p Factor tubular type. FIG. 1 shows schematically a reactor; FIGS. 2-4 are the same options; in fig. .5 - nozzle. Example 1. The process is carried out in a reactor with a stirrer, having an internal diameter of 80; mm and a length of 640 mm, provided with a guide tube with a diameter of 44 mm and a length of 320 mm, which is placed in the middle 50 mm above the bottom. The tubular reactor located in series is subdivided into thin vertical standing high-pressure pipes with
    with a diameter of 45 k and a length of 1000 mm, which are connected to each other and to a stirred reactor through pipes with an internal diameter of 10 mm (see Fig. 1). All reactors are equipped with a nozzle located in the middle. bottom to enter the reaction mixture; and in the middle of the top a short immersion submersible tube. The effective capacity of the stirred reactor is 3.18 liters, and the tubular reactors are 9.54 liters, the connecting pipes are 0.5 liters, as a result of which the total capacity of the device is 13.22 liters. After heating the contents to 170 ° C and setting the synthesis gas pressure to 280 atm, hourly continuously, 40 liters of the used mixture of olefins are injected, which consists of C and C paraffins by 72% and n-olefins with 28%. bonds in the middle position (approximately 8% of and 92% of C-olefins), in addition, 10 liters of isobutanol containing a cobalt metal in the reaction mixture 0.1 weight. and so much synthesis gas (45% by volume of CO and 55% by volume of HQ), so that in 1 hour 4 m of exhaust gas is formed. The temperature of the reaction mixture in the reactor with a mixer and in successively arranged tubular reactors is maintained at about 170 ° C. A sample is periodically taken to maintain the degree of conversion of the olefin at the exit of the stirred reactor to about 55%. When leaving the installation, a conversion rate of 97.1% is obtained. The residence time is only 0.33 hours. After separation of the reaction products in a known manner, out of every 100 mol of the reacted olefin, 82.4 mol of alcohol, 12.4 mol of paraffins and 5.2 mol of high boiling residues are obtained, based on the olefin used, alcohol yield 80.0%. The resulting alcohol has a follow-up composition (according to gas chromatography data),%: 2-butylheptanol-1 0.16; 2-propyloctanol-1 0.16; 2-ethylnonanol-1 0.30; 2-methyldecanol-1 0.83; n-undecanol-1 4.35; 2-pentylheptanol-1 5.00; 2-butyloctanol-1 8.60 / 2-propylnonanol-1 8.30; 2-ethyldecanol-1 8.50; 2-methylundecanol-1 17.20j n-dodecanol-1 46.60%.
    PRI mme R 2. Use the device according to Example 1 and operate under the same reaction conditions with the difference that the stirred reactor has an internal diameter of 80 mm, a length of 1300 mm and an effective capacity of 6.36 liters, as a result of which The total capacity of the installation is 16.40 l. If according to example 1, 40 l of olefins and paraffin mixtures of 10 l of a solution of cobalt catalyst in isobutanol, as well as synthesis gas in an amount to ensure the formation of
    4 m9 of exhaust gas, an olefin conversion degree of 71.0% is obtained at the outlet of the reactor, and the degree of olefin conversion of 97.8% is obtained from the plant. The residence time is 0.40 parts. 100 moles of olefin after the usual separation gives 81.2 moles of alcohol having a composition similar to example 1, 13.2 moles of paraffins and 5.6 moles of high boiling residues, based on olefin used corresponds to an alcohol yield of 79.6%.
    Example 3. The process is carried out according to Example 1 with the difference that after heating the system to 170 ° C and setting the synthesis gas pressure to 280 atm, 40 L of an olefin and paraffin mixture with 30% n-olefin (75% and 25% α-olefin), in addition, 10 l of isobutanol with such an amount of cobalt hydrocarbonyl that the content of metallic cobalt in the reaction mixture is 0.1 wt.% and such an amount of synthesis gas (from 45% by volume and 55% by volume Hj) that waste quantity 4. The temperature of the reaction mixture in the reactor and the connected pipelines support about 170 ° C. Upon exiting the reactor, an olefin conversion of 56.5% is achieved. When exiting the device, a conversion of 98% is determined. The residence time of 0.33 hours. Out of 100 mol of the converted olefin, 81.8 mol of alcohol, 12.5 mol of paraffins and 5.7 mol of high boiling residues are obtained after ordinary processing. This corresponds to an alcohol yield of 80.2% in terms of the olefin used. The alcohol has the following composition (according to gas chromatography data),%: 2-pentyl octanol-1 7.0; 2-butylnonanol-1 7.4; 2-propyldecanol-1 6.3; 2-ethylundecanol-1 6.7; 2-methyldodecanol-1 13.4; n-tridecanol 34.0; 2-hexyloctanol-1 + 2-pentylnonanol-1 4, OJ 2-butyldecanol-1 2,6; 2-propylundecanol-1 2.3; 2-ethyldodecanol-1 2,7; 2-methyltridecanol-1 4,3, n-tetradecanol-1 9,3.
    EXAMPLE 4 Example 1 is repeated, with the difference that 16 liters of 100% branched Cg-olefia composition,%: i, n-octenes 8; isomeric 3-mtylheptenes 45 in isomeric 5-methylheptins 10, isomeric 3,4-dimethylhexenes 37, as well as a l of a solution of cobalt bicarbonyl in isobutanol. The conversion of olefin at the outlet of the reactor 51.3%, at the output of the device 95.8%. The residence time is 0.83 hours based on 100% olefin. Of the 100 moles of reacted olefin, 80.7 moles of spiethe, 10.5 moles of the residue and 8.8 moles of paraffin are obtained. This corresponds to an alcohol yield of 77.3% based on the olefin used.
    The alcohol has the following composition (according to gas chromatography),%: isomethyloctanol 55 / isodimethylheptanol 37; isononanols 18. Isomeric alcohol separation is not possible.
    Example 5. Example 1 is repeated, but after heating the systek, 40 l of a mixture of olefin and paraffin,; containing 70% n-hexane and 30% n-gbk .senen (including hexene-1 9%, hexey-2 38% and hexene-3 "53%, in addition, 10 l of isobutanol with that amount of cobalt hydrocarbonyl, so that the content of cobalt metal in the reaction mixture is 0.1% by weight, and there is also an amount of synthesis gas (with 45% by volume of CO and 55% by volume of Hj) that the amount of exhaust gas is 4. The temperature of the reaction mixture in the reactor and in the connected pipelines, it is maintained at about 170 ° C. At the exit of the reactor, an olefin conversion of 59.5% is achieved. transformation. The residence time of 0.33 h. Of the 100 mol of unreacted olefin, 84.5 mol of alcohols, 10.0 mol of paraffins and 5.5 mol of high boiling residues are obtained after ordinary processing.This corresponds to an alcohol yield of 82.8%, in terms of used
    olefin. Alcohol according to gas chromatography has the following composition,%: n-heptanol-1 64; 2-methylhexanol-1 22; 2-ethylpentanol-1 14.
    Example b. Example 1 is repeated. The difference is that 40 l of a mixture containing up to 70% n-paraffin (namely, 1.1% HQ, -paraffin, -98.2% n-Scoc-paraffin and 0, are fed in during 1 hour) 7% n-Cd-paraffin) and up to 30% n-olefins (namely, 1.1% olefin,
    0 98.2% H-CjjQ-olefin and 0.7% n-Cd, α-olefin) with double bonds (approximately only 4% exist as its α-olefin). The degree of conversion of the olefin at the outlet of the reactor is 51.1%. When you exit 5 from the device, the conversion degree is .96.5%. The residence time is 0.33. Out of 100 mol of the reacted olefin, after ordinary processing, 78/8 mol of alcohol, 14.0 mol of paraffin are obtained.
    0 and 7.2 mol of high boiling residues. This corresponds to an alcohol yield of 76.0%, based on the olefin used.
    Alcohol has the following composition (according to gas chromatography data),%: H-ce-jji alcohol 58; 2-methyl-C o-alcohol 25; unspecified isomeric alcohols of 15.5; C, alcohols 1; C23 alcohols 0.5.
    Examples 7-12. Repeat
    0 example 2 with the difference shown in the table. The table also summarizes the results of experiments.
    The composition of the alcohol obtained in examples 7-12, similar to the composition of the alcohol according to example 2.
    Example 13. Example 2 is repeated, with the difference that the original olefin is not fed through pipeline 1, but through pipeline 2, introduced 160 mm into the reactor through the top cover (see Fig. 2). At the same time, the degree of conversion of olefins at the first stage of the process is 53%, at the second stage of the process is 96.5%. Alcohol yield
    whose composition is similar to the composition of alcohol in example 2, 82%.
     Example 14. Repeat with; measure 2 with the difference that the mixing of the starting olefins with the reaction mixture was carried out with a propeller stirrer 3 (see the attached figure 3). The degree of conversion of olefins per ml of the first stage of the process is 58.5%, and at the second stage of the process 98.5%. The yield of alcohol, the composition of which is similar to the composition of alcohol
    (5 according to example 2, 79.8%.
    Example 15. Example 2 is repeated with the difference that the initial olefins are mixed with the reaction mixture by increasing the amount of off-gas and gas to 64 nm. The degree of conversion of olefins in the first stage of the process is 52%, in the second stage of the process 95.5% . The alcohol yield, which is similar to the composition according to example 2, 78.5%.
    Example 16. Example 2 is repeated with the difference that the mixing of the initial olefins with the reaction mixture is carried out using a nozzle (Fig. 5) installed in the lower part of the reactor. At the same time, the source olefin is fed through pipeline 4, and a mixture of carbon monoxide with hydrogen is supplied via pipeline 5; At exit 6, the nozzle is narrowed to 0.09. This contraction gives the kinetic energy needed to carry out the mixing process. In this experiment, the degree of conversion of olefins in the first stage of the process is 52.5%, in the second stage of the process 96%. Alcohol yield, composition
    which is similar to the composition of the alcohol in example 2, 79,5%.
    权利要求:
    Claims (1)
    [1]
    1. US Patent No. 3118949, cl. 260-604, 01.21.64 (prototype).
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    同族专利:
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    引用文献:
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    DE888094C|1942-09-01|1953-08-31|Chemische Verwertungsgesellsch|Process for the production of oxygen-containing organic compounds|
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    US3113974A|1959-06-19|1963-12-10|Monsanto Chemicals|Oxo process with continuously increasing temperature in a continuous reactor|
    US3220998A|1961-05-04|1965-11-30|Phillips Petroleum Co|Control of exothermic process carried out in series of reactors|
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    DE3119594A1|1981-05-16|1982-12-02|Chemische Werke Hüls AG, 4370 Marl|METHOD FOR THE CONTINUOUS PRODUCTION OF ALKYLESTERS SATURED ALIPHATIC CARBONIC ACIDS|
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    法律状态:
    优先权:
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