• 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:
    Alkylene carbonates, particularly ethylene carbonate, are prepared by the reaction of an alkylene oxide with carbon dioxide in the presence of a catalyst at temperatures ranging upwards from 20 DEG C, particularly temperatures above about 90 DEG C, preferably 90-170 DEG C. The conversion of alkylene oxide to alkylene carbonate can be carried out in the presence of water while minimizing the undesirable hydrolysis of the carbonate to the corresponding alkylene glycol and formation of higher glycols. This is achieved by maintaining the water to alkylene oxide molar ratio and the carbon dioxide to alkylene oxide ratio within stated limits and adjusting the carbon dioxide partial pressure to provide the desired selectivity to alkylene carbonate.
    公开号:SU1574175A3
    申请号:SU823522506
    申请日:1982-12-01
    公开日:1990-06-23
    发明作者:Дж.Харви Роберт；М.Сакс Говард
    申请人:Сайнтифик Дизайн Кампани Инк (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the preparation of alkylene carbonates, which are used as solvents or as a source of the corresponding glycols.
    The purpose of the invention is to increase the conversion of alkylene oxide and simplify the process.
    The goal is achieved by the interaction of C C -alkylene oxide with carbon dioxide in the presence of water and iodide or methyltriphenylphosphonium bromide at 30-170 ° C, pressure of 25-104.8 kg / cm, with a molar ratio of carbon dioxide to Ca-C4 alkylene oxide, equal 1.3 to 56: 1, the molar ratio of water to
    C-C alkylene oxide equal to 0.06-4: 1, molar ratio of iodide or methyltriphenylphosphonium bromide to kilenoxide equal to 0.14-0.0013: 1, and a partial pressure of carbon dioxide equal to 24.4-65 kg / cm .
    Example 1. The implementation process at temperatures below 90 C in the absence of water.
    A sample of catalyst9 to be tested is injected into a bomb with a volume of J30 cmE, manufactured by the company Parr Instrument Company. Ethylene oxide and carbon dioxide samples were introduced at -78 ° C by immersion of a bomb in a dry ice / water bath. Then the bomb is hermetically sealed and placed in a jar with temperature
    i
    four
    H SL
     ABOUT
    36 ° C so that the temperature inside the bomb rises to 30 ° C and the reaction proceeds. Stirring is carried out by means of a magnetic disk. After a corresponding period of time, the bomb is removed from the bath and its contents are analyzed. The test results are shown in Table. J.
    x It was found that water can be present without the formation of significant amounts of glycols, provided that the temperature is sufficiently low. It was first observed that water has a beneficial effect on the selectivity of the process with respect to carbonate with the use of some catalysts, while with the use of other catalysts the selectivity of the process is suppressed.

    Example 2: Effect of water on catalysts.
    The procedure is carried out in the same manner as described in Example 1, with the difference that different amounts of water are introduced into the Parr bomb, with the results shown in Table 2.
    The data in Table 2 show that the presence of water does not significantly affect the overall conversion of ethylene oxide, but the selectivity for ethylene carbonate decreases with the use of catalyst c, while with the use of catalyst b the selectivity for ethylene carbonate increases The catalyst c is more suitable for a reaction system in which t the amount of water present is not very large. It should be noted that the molar ratio of water to ethylene oxide is about 0.55: 1, compared to the theoretical 1: 1 ratio required for the hydrolysis reaction. Catalyst b is less effective in the absence of water (test 2), but its effectiveness is manifested in the presence of water. It should be noted that when using this catalyst, the molar ratio of water to ethylene oxide reaches about 4: 1.
    Although the proposed method is especially effective in its implementation with obtaining vylelesarbonate, but
    0
    50
    five
    Q
    0 5
    five
    0
    more widely applied to other cyclic radical compounds.
    Example 3. Getting propyne, leucarbonate.
    A sample of catalyst to be tested and water (if used) is introduced into the Parr bomb.
    bone 130 cm Samples of propylene oxide and carbon dioxide are introduced at -78 ° C by immersing the bomb in a dry ice / acetone bath. The bomb is then hermetically sealed and placed in a bath at a temperature of 36 ° C so that the temperature inside the bomb increases to 30 ° C, and the reaction is carried out. After a corresponding period of time, the bomb is removed from the bath and its contents are analyzed. The test results are shown in Table. 3
    Example 4. Preparation of 1,2-butene carbonate.
    The procedure is carried out as described in Example 3, but with the introduction of 1,2-butylene oxide into the bomb instead of propylene oxide. The test results are presented in table 4.
    Example 5. A sample of the catalyst to be tested, together with water and solvents (if used), is introduced into ele. heated autoclave eml
    300 cm bone, equipped with a turbine mixer manufactured by Autoclave Engineers, Ins. Ethylene oxide and carbon dioxide samples were introduced at -78 ° C while the autoclave was immersed in a dry ice / acetone bath. The autoclave is then sealed and heated to the desired reaction temperature. After a certain period of time, the autoclave is cooled and its contents analyzed. The test results are shown in table.5. The following examples show that, in contrast to the previously known method, it is possible to obtain high yields of alkylene carbonates when carrying out the process at temperatures above 90 ° C in the presence of significant amounts of water and suppressing the formation of higher alcohols.
    Example 6. The process at a temperature above 90 ° C in the presence of water.
    A number of tests are carried out at temperatures above 90 ° C using 51
    by varying amounts of water. Ethylene oxide, carbon dioxide, water, and methyltriphenylphosphonium iodide are continuously introduced into a 1-liter high-pressure autoclave equipped with a stirrer electrically heated. Both liquid products and non-chemically converted vapors are continuously removed from the autoclave and separated into. the vapor-liquid separator located outside the autoclave. The composition of both liquid and vapor flows is determined by gas chromatography and the conversion degree and selectivity of the process are calculated. The results are presented in table.6.
    It can be seen from Table 6 that if the process is carried out even at temperatures up to 170 ° C, these high yields of ethylene carbonate can be obtained, although the amount of water present exhibits a stronger effect at 170 ° C than at 130 ° C. In fact, the results of tests 40 and 41 confirm that the conditions under which the glycol becomes the predominant product can be chosen. In each test, the molar ratio of CO2 / E0 is more than 1: 1.
    In the case where the molar ratio of CO2 / EO is less than 1: 1, completely different results are obtained, as can be seen from the following examples.
    Example 7. Effect of CO2 / EO ratio.
    The experiment was carried out as described in Example 6, test 33, with the difference that the gauge pressure is 25 kg / cm2 and the molar ratio C02 / E0 varies from 2.0 to 0.5. The molar ratio of C0g / E0 is 2, the selectivity for ethylene carbonate (EC is 63.2%, and the selectivity for ethylene glycol (MEG) is 36%, while at a molar ratio of C0g / E0, equal to 0.5, the selectivity of the process for MEG is 58% and selectivity for the EU is 41%. In addition, with a CO2 ratio of 0.5, the formation of diethylene glycol (DEG) is quite significant, so that the selectivity for DEG is 1.4%, while with a CO 2 / EO ratio of 2, the

    50
    0 5 0 5
    five
    75 The ratio of DEG is only 0.8%. Therefore, the molar ratio C04 / E0 is a very important factor if it is desirable to obtain alkylene carbonates instead of the corresponding glycol, when alkylene oxide reacts with carbon dioxide in the presence of water. In order to achieve such results, the molar ratio should be more than 1. The most appropriate molar ratio is selected depending on the amount of water present and the temperature during the process.
    Example 8. Effect of C02 partial pressure.
    The importance of partial sleep pressure from the results of tests carried out as described in Example 6, in which the absolute and partial pressures change. Results are given in ga bl. 7
    From tab. 7 it is clear that if the partial pressure of carbon dioxide is not maintained sufficiently high, the reaction will produce significant amounts of glycol, which is undesirable if the main purpose is to obtain ethylene carbonate. Therefore, the temperature, the H20 / E0 ratio and the CO partial pressure must be adjusted to achieve process selectivity with respect to the desired carbonate. For example, if the molar ratio of water to ethylene oxide in the feedstock is 1: 1 and the reaction temperature is 130 ° C, then the partial pressure of carbon dioxide 2 must be maintained at 65 kg / cm or even higher so that the maximum amount of the resulting ethylene carbonate.
    Example 9. Effect of attitude.
    In another series of tests carried out according to the description of Example 6, the amount of water varies, and the results shown in Table 2 are obtained. eight,
    The calculation of reaction rate constants shows that an increase in the conversion of ethylene oxide from 92 to 97.5% is equivalent to an increase in the reaction rate of about four times. Thus, it was first discovered that the introduction of water into dry feedstock significantly increases the reaction rate while the reaction product is mainly ethylene carbonate.
    Thus, the proposed method allows, in comparison with the known, to increase the conversion of alkylene oxide to 97.5%, which is equivalent to increasing the reaction rate by about four times, simplifies the process due to the possibility of carrying out the process in the presence of water to obtain the desired carbonates with high yield and selectivity (in a known method, this requires drying of the initial reagents).
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of producing C-C-alkylene carbonate by reacting the corresponding alkylene oxide with dioxide in the presence of a catalyst at elevated temperatures and pressures, o t
    five
    0
    In order to increase the conversion of alkylene oxide, simplify the process, Cr-C4 alkylenoxide is taken as alkylene oxide, and methyltriphenylphosphonium iodide or bromide is used as a catalyst and the reaction is carried out in the presence of water at a temperature of 30-170 ° C, pressure of 25-104.8 kg / cm2, with a molar ratio of carbon dioxide to C -C alkylene oxide equal to 1.3-56: 1, a molar ratio of water to C2-C4 alkylene oxide equal to 0.06-4: molar ratio of iodide or Methyltriphenylphosphonium bromide to Cr-C4-alkylene oxide, 0.14-0.0013: 1, and carbon dioxide partial pressure Erode equal to 24.4f C / 2
    65 kg / cm.
    Priority featured:
    02.12.87 at a temperature of 30-90 ° С, 15.11.82 at a temperature of 90-170 ° С
    carbon dioxide partial pressure
    Notes
    EO is ethylene oxide.
    EU - ethylene carbonate.
    a - trimethylsulfonium iodide, b - methyltriphenylphosphonium iodide,
    c - tetraphenylsurky bromide; d - triphenylantimony dichloride,
    e is methyltriphenylphosphonium bromide; f - tetraethylammonium bromide.
    table 2
    1574175
    10 Continuation of table 2
    1157 349
    2113 1590
    583 350
    1263
    50 70
    (mania. THF - tetrahydrofuran.
    Each test uses 20-g methyltriphenylphosphonium iodide,
    CO partial pressure, kg / cm (absolute).
    Continuation of table.5
    98.2 99.5
    95.5 96.0
    Table 6
    Table 7
    Table 8
    类似技术:
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    US4786741A|1988-11-22|Preparation of alkylene carbonates
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    US2448375A|1948-08-31|Preparation of carboxylic acids
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    US4841072A|1989-06-20|Preparation of alkylene carbonates
    US2060086A|1936-11-10|Production of carbonylic compounds
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    US4855516A|1989-08-08|Method of manufacturing 2-propyn-1-ol
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    US5023345A|1991-06-11|Preparation of alkylene carbonates
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    US1939189A|1933-12-12|Production of dioxane and its homologues
    US1733720A|1929-10-29|Manufacture of alcohol
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    同族专利:
    公开号 | 公开日
    BG48693A3|1991-04-15|
    MX163138B|1991-08-30|
    CH653984A5|1986-01-31|
    SE454088B|1988-03-28|
    NO162519B|1989-10-02|
    DE3244456A1|1983-06-23|
    NL8204661A|1983-07-01|
    GB2113207B|1986-05-08|
    AU558415B2|1987-01-29|
    NO824030L|1983-06-03|
    ES517885A0|1983-12-16|
    GB2113207A|1983-08-03|
    RO85557A|1985-03-15|
    AU9084282A|1983-06-09|
    SE8206848L|1983-06-03|
    FR2517306B1|1986-02-28|
    FR2517306A1|1983-06-03|
    BR8206977A|1983-10-11|
    IT8249611D0|1982-12-02|
    SE8206848D0|1982-12-01|
    IT1189430B|1988-02-04|
    IN159117B|1987-03-28|
    NO162519C|1990-01-10|
    DE3244456C2|1990-07-05|
    KR860001856B1|1986-10-24|
    AR231432A1|1984-11-30|
    KR840002762A|1984-07-16|
    ES8401435A1|1983-12-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE740366C|1939-03-11|1943-10-19|Ig Farbenindustrie Ag|Process for the production of glycol carbonate|
    US2773070A|1952-10-31|1956-12-04|Jefferson Chem Co Inc|Catalytic process for producing alkylene carbonates|
    US2994705A|1958-12-08|1961-08-01|Pure Oil Co|Preparation of cyclic alkylene carbonates in the presence of organic phosphonium compounds|US5138073A|1981-12-02|1992-08-11|Scientific Design Company, Inc.|Preparation of alkylene carbonates|
    US4400559A|1982-06-14|1983-08-23|The Halcon Sd Group, Inc.|Process for preparing ethylene glycol|
    US4851555A|1984-10-25|1989-07-25|Scientific Design Company, Inc.|Process for preparing alkylene oxides from alkylene carbonates|
    US4931571A|1984-10-25|1990-06-05|Scientific Design Company, Inc.|Process for preparing alkylene carbonates from alkylene oxides|
    DE4030283A1|1990-09-25|1992-03-26|Ruetgerswerke Ag|PROCESS FOR PREPARING CYCLIC CARBONATE|
    DE4105554A1|1991-02-22|1992-08-27|Bayer Ag|METHOD FOR PRODUCING DIALKYL CARBONATES|
    JP3823149B2|2002-03-06|2006-09-20|独立行政法人産業技術総合研究所|Alkylene carbonate synthesis catalyst|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US32644781A| true| 1981-12-02|1981-12-02|
    US06/441,191|US4786741A|1982-11-15|1982-11-15|Preparation of alkylene carbonates|
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