• 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:
    Crude, virtually anhydrous sec-butyl alcohol, prepared by catalytic direct hydration of n-butenes is freed from the by-products which can be distilled azeotropically and are highly volatile by continuous azeotropic distillation in a separation column by means of water, the pre-purified sec-butyl alcohol which is obtained in anhydrous form is removed and the high-boiling by-products are then separated off in a separate column. …<IMAGE>…
    公开号:SU1657053A3
    申请号:SU884356321
    申请日:1988-08-25
    公开日:1991-06-15
    发明作者:Остербург Гюнтер
    申请人:Рвэ-Дэа Аг Фюр Минералель Унд Хеми (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the purification of lower alcohols, in particular, to an improved method for the purification of crude sec-butyl alcohol.
    The purpose of the invention is to increase the degree of purification of sec-butyl alcohol.
    The goal is achieved by the method of purifying crude sec-butyl alcohol, which includes the stages of rectification, condensation and recirculation of the head product of rectification, due to the fact that the crude alcohol is fed to the 5th or 10th plate, counting from the top of the rectification column containing 55- 85 practical plates, and the rectification is carried out in the presence of water, taken in the amount of 7.6-19.7% by weight of the head product, at a temperature in the upper part of the column equal to 82.3-83.4 C, and atmospheric pressure, when the ratio of recycled head products that and crude alcohol, equal to (1, 7-2,6): 1, the ratio of the concentrations of sec-butyl alcohol and divorce-butyl ether in the azeotropic withdrawn head product, equal to (0.7-2.8) :, while maintaining plates in the middle part of the distillation column at a temperature of 89-91 ° C, and condensation is carried out after rectification.
    about cl
    Xi
    about cl with

    with
    The water required for rectification can be added either to the supplied raw alcohol or to the recirculated main product after its condensation.
    At the start of the distillation column, water is either added to the supplied raw alcohol, or introduced separately into the column. Adding water is eliminated s if the supplied crude alcohol already contains the required amount of water.
    In order to prevent the loss of sec-butyl alcohol, non-recirculated water-containing head product after condensation can be fed to the separation of sec-butyl alcohol contained in it as an aerootrope from the bottom. The azeotrope thus obtained is added to the crude alcohol before it is fed to the distillation column. In this case, no water is added to the recycled head product. Conversely, the removal of water from the system, for example, by reducing the water content in the recycled overhead product, may be required.
    In the described purification method, preference is given to using crude alcohol obtained by direct hydration of n-butenes on an acidic cation exchanger,
    The following examples illustrate the invention, which can be carried out in installations according to FIGS. 1-A.
    Example 1 (aus) (installed in the installation according to figure 1; figure 3 shows the condensation unit in figure 1).
    1663 kg / h obtained by direct hydration of n-butenes on the acid cation exchanger of crude sec-butyl alcohol containing 23.8 kg / h of tert-bu type alcohol, 96.1 kg / h of double-butyl ether and 36.8 kg / h of hydrocarbons Cd, pipeline 1 is continuously fed to the 75th plate of the column 2, which contains a total of 85 real plates, i.e. on the 10th plate, counting from the top of the column. In the upper part of the column 2, 3180.5 kg / h of recycling, consisting of 1257.2 kg / h of sec-butyl alcohol, 204.8 kg / h of tert-butyl alcohol, 781.3 kg / h of divor butyl ether, 299.0 kg / h of Ca hydrocarbons and 638.2 kg / h of water. At a temperature in the upper part of the column equal to 83 ,, the temperature on the 35th plate, equal to 5 ° C (set using controller 3),
    five
    0
    five
    0
    five
    0
    five
    0
    five
    the ratio of recycled head product and crude alcohol, equal to 1.9: 1, the ratio of the concentrations of sec-butyl alcohol and divorce-butyl ether, equal to 1.6: 1, and the presence of water in the amount of 18.3% of m.chg- The head product of the pipeline 7 removed 3487.3 kg / h of azeotropic head product consisting of 1407.3 kg / h of sec-butyl alcohol, 228.6 kg / h of tert-butyl alcohol, 877.4 kg / h of divtor -butyl ether, 335.8 kg / h of CgH hydrocarbons 638.2 kg / h of water. The azeotropic head product is fed to condensation to a separator 8, from where 331.3 kg / h of the organic phase, consisting of 150.1 kg / h of sec-butyl alcohol, 23.8 kg / h of tert-butyl alcohol, is withdrawn via line 9, 96.1 kg / h of divoric butyl ether, 36.8 kg / h of Gf hydrocarbons and 24.5 kg / h of water, and 3180 kg / h of the specified composition phase, which includes 24.5 kg / h of water, is recycled through pipeline 5 supplied through the pipeline 6 (instead of water discharged in the composition of the organic phase).
    Through conduit 13, 99.7 kg / h of purified sec-butyl alcohol containing 0.01% by weight of water, 0.001% by weight is withdrawn. tert-butyl alcohol and CO, 001 wt.% divorobutyl ether. In addition, it contains another 0.1% by weight of high boiling point by-products, which can be removed in the subsequent purification step.
    Example 2. Example 1 is repeated, with the difference that the rectification is carried out at a temperature in the upper part equal to 82.3 C and the ratio of sec-butyl alcohol and divorce-butyl ether equal to 0.76: 1 in the presence of water, taken in the amount of 7.6% by weight of the head product, and on the 35th plate the temperature is maintained at 89 ° C. A purified sec-butyl alcohol of the same quality as in Example 1 is obtained.
    Example 3. Example 1 is repeated with the difference that the rectification is carried out at a temperature in the upper part equal to 82.6 ° C and the ratio of sec-butyl alcohol and divorce-butyl ether equal to 1, 65: 1 in the presence of water , taken in the amount of 11% of the mass of the head product, and on the 35th plate the temperature is maintained at 89. A purified sec-butyl is obtained.
    alcohol of the same quality as in example 1.
    Example 4. Example 1 is repeated, with the difference that the rectification of npo-j is carried out with 55 actual plates for the column under the following conditions.
    On the 45th plate, i.e. on the 10th plate, counting from the top of column 2, crude sec-butyl alcohol containing 2.4% by weight of tert-butyl alcohol, 2.5% by weight of divorce-butyl ether and 1.1% by weight of Cg hydrocarbons is fed , and the rectification is carried out at a temperature in the upper part equal to 83.4 ° C, a ratio of sec-butyl alcohol and divoro-butyl ether equal to 2.5: 1 and the ratio of recycling and crude alcohol equal to 2.6: 1 in the presence of water, taken in the amount of 19.7% by weight of the head product. At the same time, on the 25th plate, the temperature is maintained at 89.5 ° C. Get purified sec-butyl alcohol of the same quality as in example 1.
    Examples 5-12. Example 1 is repeated with the changes indicated in the table.
    Example 13 (carried out according to Fig. 2; Fig. 4 shows the condensation unit of Fig. 2).
    Example 1 is repeated, with the difference that the sec-butyl alcohol contained in the by-product stream withdrawn from the separator 8 is recovered and, as an azeotrope in the amount of 212.8 kg / h (water content 28% by weight), is added to the crude alcohol via line 14 . In this case, the water supply with the azeotrope stream of sec-butyl alcohol through conduit 14 exceeds the water withdrawal from the by-product flow through conduit 9, so that the separator 8 is additionally removed from the aqueous phase through conduit 29, and no more water is added through conduit 6 is. The flow in line 29 consists of 35 kg / h of water, 3.2 kg / h of sec-butyl alcohol, and 0.8 kg / h of tert-butyl alcohol.
    In this case, proceed as follows.
    , 1663.7 kg of a crude alcohol of the composition indicated in example 1 and 212.8 kg of a water azeotrope of sec-butyl alcohol with 59.5 kg of water are served together hourly together in a column 2. In addition, 3564.7 kg / h are fed as recycling, consisting of 1437.9 kg / h sec-butyl
    $ 0 5
    0
    d c Q
    ,
    five
    second alcohol, 224.7 kg / h of tert-butyl alcohol, 895.8 kg / h of divorbutyl ether, 342.8 kg / h of C hydrocarbons and 663.5 kg / h of water. The rectification is carried out with the ratio of recycling to crude alcohol equal to 1, 9: 1, and with the ratio of sec-butyl alcohol to di-sec-butyl e-alcohol equal to 1.6: 1, in the presence of water, taken in the amount of 18.4 % of the main product.
    3934.2 kg of azeotropic head product, consisting of 1591.2 kg / h of sec-butyl alcohol, 248.5 kg / h of tert-butyl alcohol, 991.9 kg / h of divorbutyl ether, 379.6 are obtained hourly. kg / h of Cg hydrocarbons and 723.0 kg / h of water, which in the separator 8 are divided into a light organic phase (3410.4 kg / h) and a heavy aqueous phase (529.8 kg / h).
    From the separator 8, 330.5 kg of an organic phase consisting of 150.1 kg / h of sec-butyl alcohol, 23.0 kg / h of tert-butyl alcohol, 36.1 kg / h of divorce-butyl ether, 36.8 kg / h of hydrocarbons Cg and 24.5 kg / h of water, and through the pipeline 29 - 39.0 kg of the aqueous phase, consisting of 35.0 kg / h of water, 3.2 kg / h butyl alcohol and 0.8 kg / h tert-butyl alcohol.
    Using an adjustment valve 12, 3,664.7 kg of heterogeneous recycling of the indicated composition is recycled hourly from the separator 8 through the pipeline 5 back to the column.
    In extractor 15, with the help of 1678.0 kg / h of water supplied through conduit 16, all water-soluble components, in particular sec-butyl and tert-butyl alcohols, are removed from the effluent from the by-product stream through conduit 9. Through conduit 18, all water-insoluble by-products, such as divoric butyl ether and dimers, are withdrawn from the plant.
    1914.6 kg of the mixture (1737 kg / h of water, 153.3 kg / h of sec-butyl alcohol and 23.8 kg / h of tert-butyl alcohol), obtained from the alcohol-containing leaching stream discharged through line 19, are hourly supplied to the column 17 water and the aqueous phase discharged through pipe 29, where the alcohols contained in it as the blend of the corresponding alcohols of binary azeotropone with water discharged through pipe 20 are separated from the excess water and in an amount of 239.8 kg / h are discharged through pipe 21. This the flow consists of 153.3 kg / h sec-butyl alcohol, 23.8 kg / h tert-butyl alcohol and 62.7 kg / h of water.
    Using the control valve 22, a recycle is fed through the pipe 23 at a reflux ratio of about 1: 1 in terms of the flow in the pipe 21, which ensures a sufficient separation between the azeotrope and water.
    The flow of azeotrope of alcohol with water through the pipeline 21 is fed to the column 24 for distillation. 27.0 kg of boiling point (8 ° C) below the boiling point of aseotrope of sec-butyl alcohol and submersible (87.5CC) of azeotrope of tert-butyl alcohol (23.8 kg / h) and water are withdrawn through line 25 and output from the process via pipeline 26. Using an adjusting valve 27, through pipeline 28, the amount of recycle is supplied to column 24, providing a stack of separation in the column, preventing or maintaining, within the desired limits, loss of sec-butyl alcohol removed by pipeline 26 or recirculation secondary spirits through the pipeline 14. In this way, the entire withdrawn from the separator 8 of the column 2, sec-butyl alcohol can be recycled to the column 2 with virtually no losses.
    Due to the limited and as a result of the presence of non-polar byproducts of still reduced water solubility, the flow of conduit 9 contains less water (24.5 kg / h) in terms of sec-butyl alcohol than in flow of conduit 14 (59.5 kg / h on 10
    15
    a drain (through conduit 5) flows as flow through from the inflow chamber, from where this phase can be diverted through conduit 9. The separated in the inflow chamber of the heavy phase is prevented by direct removal of the light phase from the inflow chamber through conduit 5, and thus, the amount of water contained in the stream of pipeline 7 and added through the pipe to pipe 6 is immediately recycled to column 2 as part of a heterogeneous mixture with a light phase.
    In contrast to this, in the case of using the separator of FIG. 4 t, the conduit 5 is introduced into the inflow chamber d of a level corresponding to about 5 of the partition height. On the one hand, this exercise provides a separated and diverted heavy water-rich phase. On the other hand, at the interface between the heavy and light phases, i.e. On the side of the pipeline feed injected into the chamber, the amount of reflux installed by means of an adjusting valve 12 to column 2 is directly recycled in the form of such a composition, which is obtained from the difference of the light phase between the amount at the current (through line 7) and flow into the pipeline 9 and from the difference between the heavy phase in the tributary (pipe 7 of water) and water discharged through line 29.
    The resulting aqueous phase equilibrium with the light organic phase in line 29 contains sec-butyl alcohol in dissolved form, for the recovery of which the stream is added directly to the stream fed to column 17. The water contained in line 29 is recycled to column 2. composed
    20
    25
    thirty
    35
    ten
    dy) formed by the azeotropic co-product of the column 24 discharged through the pipeline 14.
    tavu sec-butyl alcohol and water. Therefore, through the pipe 29 by means of the adjusting valve 30, water is continuously removed.
    To this end, instead of the separator 8 in figure 3, used in the installation of figure 1, use the separator 8 in figure 4. In the case of using the separator 8 of FIG. 3, the container, for example, of a cylindrical shape, is divided by a partition into two chambers so that the amount of light organic phase representing the difference between the inflow (through line 7) and

    ten
    15
    70538
    a drain (through conduit 5), flows as flow from the inflow chamber to the drain chamber, from where this phase can be diverted through conduit 9. The separation in the inflow chamber of the heavy phase is prevented by direct removal of the light phase from the inflow chamber through conduit 5, and thus In this way, the amount of water contained in the flow of pipeline 7 and added through pipeline 6 is immediately recycled to column 2 as part of a heterogeneous mixture with a light phase.
    In contrast, in the case of using the separator of FIG. 4, pipe 5 is introduced into the inflow chamber to a level corresponding to about 50% of the height of the partition. On the one hand, this measure provides for the separation and withdrawal of the heavy water-rich phase. On the other hand, at the dividing line between the heavy and light phases, i.e. At the upper edge of the inlet line introduced into the chamber, the amount of reflux installed by adjusting valve 12 to column 2 is directly recirculated as such a composition, which is obtained from the difference of the light phase between the amount of inflow (through line 7) and the flow to pipeline 9 and from the difference heavy phase in the tributary (through line 7) and water discharged through line 29.
    The resultant equilibrium with the light organic phase, the aqueous stream in line 29 contains sec-butyl alcohol in dissolved form, for the recovery of which the stream is added directly to the stream fed to the column 17. The water in the pipeline 29 is recycled to the column 2
    20
    25
    thirty
    35
    ten
    the bottom product of the column 24,
    Pipeline 14.
    Purified by line 13 purified sec-butyl alcohol (72.3 kg / h) has the same quality as the alcohol purified in example 1.
    The proposed purification method allows to obtain sec-butyl alcohol containing 0.01 wt.% Water, .Ј0.001 wt.% Tert-butyl and 0.001 wt.% Divorbutyl ether versus 0.035 - 0.07 wt. % of water, 1% by weight of divorce-butnol ester, as well as other impurities during purification by a known method.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of purification of raw sec-butyl alcohol, which includes the stages of distillation, condensation and recycling of the head product of rectification, which is characterized by the fact that, to increase the degree of purification, the crude alcohol is fed to the 5th or 10th plate, considered from the top of the rectification column with 55-85 practical stoves, and the rectification is carried out at
    I
    temperature in the upper part of the column, equal to 82, 4 ° C, and atmospheric pressure in the presence of the bottom, taken in an amount of 7.6-19.7% of the mass of the head product, with a ratio of the recirculated head product and crude alcohol equal to 1.7-2.6: 1, the ratio of the concentrations of sec-butyl alcohol and divorce-butyl ether in the azeotropic offal head product equal to 0.7-2.8: 1, and while maintaining the plate in the middle part of the distillation column 89-91 ° C, and condensation is carried out after rectification.
    Conditions and results of purification of sec-butyl alcohol in examples 5-12
    Total plates 55
    Tributary plate50Weatheat
    plate 25Submitted
    crude alcohol,
    l / h1,5
    Recycle amount, l / h 2,6
    The ratio of recycling and crude alcohol1,7
    The ratio of weight and dbbe in the main product0, 7
    The main by-products in crude alcohol, wt.X:
    TBS 0.8 LVBE 1.3
    The main by-products in purified alcohol, wt.X:
    , 2
    , 2
    Note: sec-butyl alcohol; divorce-butyl ether; tert-butyl alcohol.



    55
    45-
    25-
    1.0
    2.6
    2.6 2.3
    55
    45-25-
    1.0 2.6
    2.6 2.8
    85
    75-
    45-
    1.0 1.9
    1.9 2.0
    85
    75-
    45-
    1.0
    1.7
    1.7 2.0
    2.4 2.6
    2.6 0.9
    1.8 1.3
    1.8 1.3
    , 001 / 0.001 Ј0.001, -. 0.001 40.001 0.001 0.001 0.001 Ј.0.001, 0.001
    Qb.3
    FIG.
    &
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    引用文献:
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    US2788315A|1952-12-04|1957-04-09|Exxon Research Engineering Co|Purification of c4 to c6 alcohols by extractive distillation|
    US2875138A|1955-01-17|1959-02-24|Exxon Research Engineering Co|Purification of secondary butyl alcohol|
    DE1017602B|1956-01-16|1957-10-17|Exxon Research Engineering Co|Process for purifying raw secondary butyl alcohol|
    US2915462A|1956-07-02|1959-12-01|Union Oil Co|Distillation column control|
    GB829424A|1956-08-16|1960-03-02|Shell Res Ltd|Improvements in or relating to the purification of secondary butyl alcohol|
    DE1219011B|1963-11-22|1966-06-16|Basf Ag|Process for the purification of alkanols with 3 to 5 carbon atoms|
    US3528891A|1966-10-11|1970-09-15|Basf Ag|Purification of n-alkanols having four to five carbon atoms|
    BE755564A|1969-09-02|1971-03-01|Exxon Research Engineering Co|SECONDARY BUTANOL PURIFICATION PROCESS|
    DE2429770C3|1974-06-21|1981-04-16|Deutsche Texaco Ag, 2000 Hamburg|Process for the production of lower alcohols by direct catalytic hydration of lower olefins|
    DE3040997C2|1980-10-31|1983-07-21|Deutsche Texaco Ag, 2000 Hamburg|Process for the continuous production of sec-butyl alcohol|US5639355A|1995-03-13|1997-06-17|Texaco Chemical Inc.|Method for enhancing the yield of tertiary butyl alcohol in a tertiary butyl alcohol recovery process|
    KR20030088211A|2002-05-13|2003-11-19|재원산업 주식회사|refining method of n-Butanol|
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    JP2007230935A|2006-03-02|2007-09-13|Idemitsu Kosan Co Ltd|Purification method and production method of secondary butanol|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19873728428|DE3728428A1|1987-08-26|1987-08-26|METHOD FOR DISTILLATIVE CLEANING OF RAW SEC-BUTYL ALCOHOL|
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