• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    A process for separating indole from a mixture of indole with at least one hydrocarbon or its derivative which comprises the steps of contacting the mixture with a faujasite structured zeolite to selectively adsorb indole on the zeolite and contacting a desorbent A selected from the group consisting of C2-10 aliphatic or C7-10 aromatic ether compounds, C2-10 aliphatic ester compounds and C3-10 aliphatic ketone compounds with the indole-adsorbed zeolite to separate indole and the process which comprises, in addition, the step of contacting at least one desorbent B of the formula, <IMAGE> wherein R1 is a C1-3 alkyl group, and R2 is a hydrogen atom or a C1-3 alkyl group, with the indole-adsorbed zeolite prior to the contact of the desorbent A with the indole-adsorbed zeolite.
    公开号:SU1391498A3
    申请号:SU803001099
    申请日:1980-11-03
    公开日:1988-04-23
    发明作者:Такасо Кендзи；Хиракава Кейзо；Нисимару Хиродзи；Хонда Макото
    申请人:Асахи Касеи Когио Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    (21) 3001099 / 23-04 (22) 03.11.80
    (31)) A1215 / 79, 13532/80
    (32) 02.11.79, 08.02.80
    (33) JP
    (46) 04.23.88. Bksh. Number 15
    (71) Asahi Kasey Kogyo Kabusiki Kais (JP)
    (72) Kenji Takaso, Keyo Hirakawa, Hiroji Yishimaru and Makoto Honda (JF)
    (53) 547.752.07 (088.8)
    (56) US Patent No. 2985589, cl. 210-34i 1961.
    Koks Kbim., 1978, 4, p.34-37.
    (54) METHOD FOR INDOL ISOLATION (ITS OPTIONS)
    (57) The invention relates to the production of indole (IN), in particular, the injection of IN from indole-containing mixtures, and makes it possible to simplify the isolation process and increase its efficiency. Isolation is carried out from a mixture in which there can be at least one of the compounds selected from the group: naphthalene, thionaphthalene, 1- or 2-methyl-naphthalene, 2,6- or I, 5-dimethylnaphthalene, acetonaphthene, diphenyloxide, fluorine. The mixture with IN is subjected at 70-120 ° C to sorption using a type X or Y zeolite, followed by desorption with a desorbent solvent (DS-A). We use a 1Y type X cation exchanger that contains one of the cations of metals of group I
    Periodic system (PS) of the amount of 76.3-99.3% or group II of the PS in the amount of 61.1-77%, and the cation exchanger of the Y type contains cations of one of the metals of Group I of the PS in the amount of 66.2-99.4Z or metals of group II PS in the amount of 60-66%, and the remaining cationic sites are occupied by the cation of Na and / or hydrogen. In the third case, a cation exchanger of type X or Y contains Na cations. The cations of metals of Group I of the PS include Si, K, Rb, Cs, A ,; Group II PS - Mg, Ca, Sr, Ba, Cd. The desorbent is a solvent selected from the group: di-n-butyl ether, anisole, ethyl acetate, isopropyl ether, n-butyl acetate, iso-amylacetate, methyl ethyl ketone, methyl isobuty. Glyketone, 2-octanone, cyclohexanone. Another variant of the method involves contacting the initial mixture in the indicated modes with DS-A and a type X or Y zeolite of the indicated composition, and then carrying out the desorption first with the aid of a desorbent of the formula 1
    where R, - C, -C3-alkyl; H - H or C ,, - Cj-alkyl, and then DS-A. The method provides a degree of allocation of an IN 95.3-100%. 2 sec. f-ly, 14 ill., 7 tab.
    WITH
    co; o
    four
    with oo
     cm
    This invention relates to an improved process for isolating an indole from a mixture thereof with at least one compound selected from the group consisting of naphthalene, thionaphthalene, 1-methylnaphthalene, 2-methylnaphthalene, biphenyl, 1,5-dimethylnaphthalene, 2, 6-dimethylnaphthalene, acetonaphthene, diphenyloxy, fluorine.
    The aim of the invention is to simplify and improve the efficiency of the selection of indole from this mixture.
    Figures 1-14 are graphs explaining the proposed method.
    Example I. In a box in nitrogen atmosphere, 1 g of powdered X-zeolite calcined at 500 ° C for 2 hours and cooled in an exsiator with 2 g of a mixed solution containing, in wt.%: 2-methylnaphthalene, is contacted 5.8; indole 5.2; toluene 89.5 as a diluent, for a period of 2 hours.
    When calculating the selectivity for changing the composition of a 2-methylnaf composition, the weight of the solute before absorption,
    It) 1
    mnlo
    talina and indole K,
    I mttl
    (set U l ftoli and
    The selectivity of the adsorbent for Judah as compared with desorbent A) is equal to 98 and 96.5 mg / g of zeolite.
    Then, 0.5 g of acetonitrile is added to this mixed solution and the contact with the zeolite is carried out for 2 hours at. By the amount of desorbed indole, the calculated D is equal to 95.3%.
    EXAMPLE 2: Using industrial Y-type and A-type zeolites (FOR, 4A and 5A), characterized by an 80-120 mesh particle distribution, the
     Lrgidnafte.lin is UNIQUE LICENSE
    measure 1, and D are measured with promoted Y-type zeolite.
    The results of the experiments in example 2 are shown in table 1.
    Adsorption capacity to is defined by
    The weight of the solution in the liquid phase, which is in equilibrium with the zeolite phase after adsorption,
    mg
    The weight of the zeolite after calcination, g
    The amount of desorption of indole D is the quantity of acetonitrile desorbent, around the amount of indole, which desorbers a strong adsorption, and. of zeolite when added to ka is determined by the expression
    Weight of indole desorbed from zeolite after 2-addition of acetonite 2
    The weight of the indole adsorbed on the zeolite, before adding acetonitrile
    Relative concentration of
    iJSfl22§ 2 2SISS§ 2S2y S ° I2SS i opt
    Indole weight + other substances in
    indole-containing effluent
    The phytosite zeolites used in the examples are commercially available X- and Y-type zeolites having particles of 80-120 mesh in diameter and sodium ions as metal ions.
    Examples Zi4. The procedure of Example I is repeated, except that a solution containing, in wt.%: Diphenyl, 6.0; indole 6.0; is based on the formula
    luol 88.0, which is a diluent, and industrial U-zeolite is also used.
    INAOL
    Measured values of K and
    and are given in table 2.
    Examples 5-20. The ion exchange centers of the npOMhmmeHHoro X-zeolite are replaced by metal ions, for which X-zeolite is treated three times with aqueous nitrate or hydrochloric acid.
    31391
    metal ion 2n. ionic concentration at 70 ° C for 4 h, then the zeolite subjected to ion exchange, washed with a sufficient amount of water and dried for 6 h. The resulting zeolite was calcined at 500 C for 2 h and cooled in a desiccator. Analogously to example 1, measure
    INAO / t
    K ,, W and D.
     NOFLT KN
    ten
    The data obtained are given in table.3.
    Examples 21-36. Ion exchange is carried out in a manner analogous to Examples 5-20 using industrial INL
    Ny zeolite, Ci D from 2- / yeti lkaftek l in
    measured as in Example 1.
    The results are shown in table 4.
    Examples 37-46. In a box in nitrogen atmosphere, 1 g of industrial X- or Y-zyolite is contacted in the form of a powder calcined at ZOO C for 2 hours and cooled in a desiccator, the ion exchange centers being replaced by lithium, sodium, potassium rubidium or cesium ions, with 1 g of toluene at 70 ° C for 2 hours and then a mixed solvent containing 10% by weight of toluene is added to the mixture. Starting from this moment, the change in the amount of C indole adsorbed on the zeolite with time is measured as zero. Figures 1 and 2 show the kinetic curves of the adsorbed amount of C indole divided by the adsorbed amount of Cd, indole after at least 3 hours, as a function of time.
    The values of the curves in FIGS. 1 and 2 are listed in Table 5.
    From figure 1 and 2 it follows that the rate of adsorption is much higher than Y-zeolite with lithium ion or sodium ion compared with other zeolites.
    Examples 47-56. In a box under nitrogen atmosphere, 1 g of powdered Y-zeolite, substituted by lithium ions, is contacted with 2 g of a mixed solution containing, in wt%: indole 5.0; desorbent A 5.0; toluene 90 as a diluent, at 70 ° C for MNAOLOL
    2 h. Selectivity K d is calculated by changing the composition of the indole and desorbent.
    The results are shown in tab.
    0

    0
    5 oh,
    s
    five
    0
    4984
    Example 57: A vertical cylindrical glass column with a diameter of 8 mm and a height of 1000 mm is filled with an impermeable X-zeolite to a height of 950 mm. Keeping the temperature of the column, anisole was introduced through one end of the column at a rate of 0.5 ml / min until the column was filled with anisole. When anisole begins to flow from the other end of the column, it is stopped to feed to the column. 11.0 g of a mixed solution is fed, containing, in wt%, 2-methylnaphthalene 40; indole 10; toluene 50j at a rate of 0.5 ml / min and anisole is again fed into the column at a rate of 0.6 ml / min. before elution from the column of 2-methylnaphthalene and indole. The effluent is collected with 1-3 ml fractions for 3-6 minutes and these fractions are then analyzed.
    From the graphs (fig. 3) of the dependence of the concentration of 2-methylnaphthalene and indole in the outflowing stream from the weight of the collected outflowing stream, starting from the moment the mixed solution is introduced, it can be seen that there is a separation of the indole from 2-methylnaphthalene.
    Example 58. The procedure of example 57 is repeated with the difference that instead of industrial X-zeolite, industrial Y-zeolite is used and instead of the mixed solution of example 57, a mixture consisting of 97% by weight of 1-methylnaphthalene and 3% by weight is used. indole. The temperature of the column support 90 C.
    From the graphs (Fig. 4) of the dependence of the concentration of 1-methylnaphthalene and indole in the effluent from the weight of the collected effluent, it can be seen that the 1ddol is separated from 1-methylnaphthalene.
    PRI me R 59. A column similar to that used in Example 7 was filled with Y-zeolite replaced with lithium ions, and the column temperature was maintained at 70 ° C. Through one end of the column, n-butyl acetate is fed at a rate of 0.5 ml / min until the column is filled with the indicated ester. Then in the column serves 25.8 g of a mixed solution containing, wt.%: 2-methylnaphthalene 40; indole 10; toluene 50, the feed being carried out at a rate of 0 ml / min and then n-butylstatat is again fed at the same rate of 0.5 ml / min.
    five
    From the graphs (figure 5) of the dependence of the concentration of 2-methylnaphthalene and indole in the effluent from the weight of the effluent it can be seen that there is a separation of the indole from 2-methylnaphthalene.
    Example 60. Using a column similar to that used in Example 57 and filled with a Y-zeolite with lithium ions, maintain it at 70 C. Anisole is fed at one end of the column at a rate of 0.5 ml / min until the column is filled with anisole. Then, 22.0 g of a mixed solution of toluene and coal tar fractions with a boiling point of 220-270 ° C, which was washed with 10% sulfuric acid and then with 10% aqueous solution, are fed into the column at a rate of 0.5 ml / min. sodium hydroxide. Mixed solution contains, wt.%:
    Naphthalene
    Thionaphthalene
    1-Methylnaphthalene
    2-Methylnaphthalene
    .Cyphenyl
    1,5-Dimethylnaphthalene
    1,7-Dimethylnaphthalene
    2,6-Dimethylnaphthalene
    Indole
    Acetonaphthene
    Diphenyl oxide
    Fluoren
    Toluene
    Rest
    Anisole is then re-fed at a rate of 0.5 ml / min, up to the elution of the indicated substances. The effluent is collected in separate fractions of 1-3 ml / min and these fractions are analyzed.
    From the graphs (Figures 6-8) of the dependence of the concentration of substances in the outlet stream on the weight of the collected fractions of the effluent stream, it can be seen that the indole is separated from other substances.
    EXAMPLE 61 Using a column similar to that used in Example 57, it is filled with lithium ion Y-zeolite in a manner similar to that described in Example 57. The column is maintained at 7 ° C and anisole is fed as desorbent A through one end. } Tc at a rate of 0.5 ml / min until the column is filled with anisole. After the anisole begins to flow out of the other end of the column, the flow of this desorbent is stopped and
    19.4 0.8 3.7 5.7 1.0 0.5
    1L 0.9 1.6 3.1 2.3 0.9 56.3 2.3
    0
    five
    five
    one
    0
    0
    five
    0
    five
    0
    five
    4986
    15.0 g of a mixture of 97% by weight of 1-methylnaphthalene and 3% by weight of indole are fed at a rate of 0 ml / min and then 20 g of toluene as desorbent B at a rate of 0.5 ml / min, and then again anisole is fed at a rate of 0 ml / min up to the indole elution.
    From the graphs (Fig. 9) of the dependence of the concentration of 1-methylnaphthalene and inzole in the effluent from the weight of the effluent collected, it can be seen that the relative concentration reaches almost 100% in the concentrated part.
    Examples 62-64. The procedure of Example 61 is repeated, except that desorbent B is used instead of toluene.
    The results of the experiments in examples 62-64 are given in table.7.
    From FIGS. 10-12, it follows that high purity indole is isolated.
    Example 65. The procedure of Example 61 is repeated, except that instead of this mixture, 15.7 g of coal tar fraction with mp. 220-270 ° C, washed with 10% sulfuric acid and then with 10% aqueous solution of sodium hydroxide, instead of 20 g using 19.1 g of toluene.
    The composition of coal tar, May.%:
    Naphthalene7,9
    Thionaphthalene1,5
    1-Methylnaphthalene14.4
    2-Methylnaphthalene39,2
    Diphenyl7,9
    1, 5-Dimethylnaphthalene3,4
    1, 7-Dimethylnaphthalene5,7
    2,6-Dimethylnaphthalene4,2
    Indol3,6
    Acetonaphthene5,7
    Biphenyl oxide4,1
    Fluoren0.4
    The rest2,1
    From the graphs (Figs. 13 and 14) of the dependence of the concentration of the separated substances in the effluent on the weight of the collected effluent it can be seen that the indole is separated from other substances.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    I. A method for isolating an indole from an indole mixture with at least one compound selected from the group.
    7
    containing naphthalene, thionaphthalene, 1-methylnaphthalene, 2-methylnaphthalene, bi-phenyl, 1,5-dimethylnaphthalene, 2,6-dimethylnaphthalene, acetonaphthene, diphenyl oxide, fluorine, characterized in that, in order to simplify and increase the efficiency of isolation of indole from this mixture, the latter at 70-120 ° C is brought into contact with X-type zeolite, in which the ion-exchange cation sites are occupied by a cation selected from Group I metals of the Periodic Table of the Elements, including lithium ions, potassium, rubidium , cesium and silver in the amount of 76.3-99.3%, or from metals of group II Periodic 61.1-77.0% of the system of elements including magnesium, calcium, strontium, barium and cadmium ions, with a hydrogen ion or their mixture, or with a Y-type zeolite, in which the ion-exchange cationic sites are occupied by a cation selected from metals of group I of the Periodic system of elements, including lithium, rubidium, cesium and silver ions in the amount of 66.2-99, A%, or from metals of group II of the Periodic system of elements.

    including magnesium, calcium, stron-ion ion exchange cation sites, barium and cadmium in the amount of 60.0-66.0%, and the remaining ion-exchange cation sites are occupied by sodium cation, hydrogen ion or their mixtures, or with zeolite X -type or Y-type zeolite, in which ion-cationic sites are essentially occupied by sodium cation, and then desorbent A, selected from the group consisting of di-n-butyl ester, anisole, ethyl acetate, isopropyl ether, n-butyl acetate, isoamylacetate , methyl ethyl ketone, methyl isobutyl ketone, 2-octanone, cyclohexanone, con aktiruet zeolite, adsorbirovavschim indole.
    2, Method for isolating indole from a mixture of indole with at least one compound selected from the group consisting of naphthalene, thionaphthalene, 1-methylnaphthalene, 2-methylnaphthalene, biphenyl, 1, -5-dimethylnaphthalene, 2,6-dime - tilnaphthalene, acetonaphene, diphenylene oxide, fluorine, which differs
    the fact that, in order to simplify and improve the efficiency of the separation of the indole from this mixture, the latter is brought into contact with desorbent A and X-type zeolite, in which the ion-exchange cationic sites are occupied by a cation selected from metals
    Group of the Periodic Table of the Elements, including lithium, potassium, rubidium, cesium and silver ions in the amount of 76.9-99.3, or from Group II metals of the Periodic Table of the Elements, including magnesium, calcium, strontium, barium and cadmium in the amount of 61, 1-77.0%, and the remaining ion-exchange cationic sites are occupied by sodium cation, hydrogen ion or a mixture thereof, or a Y-type zeolite, in which ion-exchangeable cationic sites are occupied by a cation selected from metals of group I of the Periodic Table of the Elements including lithium ions , potassium, rubidi, cesium And silver in a quantity of 66.2-99.4% or from metals
    Group II of the Periodic Table of the Elements, including magnesium, calcium strontium, barium and cadmium ions in the amount of 60.0-66.0%, and the remaining
    five
    0
    you are sodium cation, hydrogen ion, or mixtures thereof; or with an X-type zeolite or Y-type zeolite, in which the ion-exchange cationic sites are occupied by sodium cation, followed by successive desorption, first with desorbent B, of the general formula
    RI
    40
    where R is —C, —C — alkyl;
    R, is hydrogen or C, -Cj-alkyl, and then again with desorbent A, selected from the group consisting of di-n-butyl ether, anisole, ethyl acetate, isopropyl ether, n-butyl acetate, isoamyl acetate, methyl ethyl ketone, methyl isobutyl ketone, 2 octanone, cyclohexanone.
    Priority points:
    02.11.79po item 1
    08.02.80po p.2.
    139149810
    Table 1
    I 10
    1.00 1.01 1.01
    3 Industrial X-zeolite 105
    4 Industrial Y-Zeolite 116
    100
    table 2
    86.6 78.1
    Tabli.tsa3
    13 Table 5
    1391498
    64 Isopropylbenol 25.0
    Table 6
    20.3
    12
     "
    BpCMfl, V
    "about
    1
    12
    Time h
    Figg
    yo
    | "A I
    30W
    E / (H) ent, g Figure 3
    80
    5G
    I
    "I
    g Yu
    go
    JOto 50
    Eluent, g
    FIG.
    2 - MeinuAHaipmaAUH
    1 etilnaftdlin
    Indole
    60
    70
    SO
    I
    I
    g
    g 60
    Zo
    thirty
    15
    I 5
     five
    20 30
    2- MemuAHocfsmaAijH
    Ying & ol
    SO
    E / (N} ent. G
    Fiz. S
    Naphthalene
    2- Methylmaphthalene / - Methylnoftglin
    NDOA
    SO 60
    Zluent z
    Fi9.6
    70
    80
    90
    3r
    ltdu emilno pfJVl
    AUH
    Bidoenil TuoHa (pmffAUH
    2.6 -QuMemuA Hotpm / iuH
    1.5 - uMsmuA - Naphthalene
    20
    30 0 50 Elnze t, z
    FIG. one
    Au etonasrten
    Dipheny / iwcud
    F / Guo / Uen
    .one
    20 30W Sro607O
    EluRn / tg g
    FIG. at
    ff / iS /}
    60
    70
    80
    EO
    indole
    80
    90
    SO60
    Elyu / t, Z .9
    t I
    I I
    about
    100
    I
    Anisol 1-Yetilynosrtaline p-Yasilol I
    X --I
    40
    50
    60
    11
    ;
    Anisol 1-NetilnadetaAin Iuopropilde l |
    Anisole
    50 5
    708030
    Eluent, g
    100
    -di
    thirty
    h
    IS
    .N 20
    S
    : sI
    "
    I
    ten
    20
    thirty
    go
    2 - Methylnasr / Palin
    1 - f emuAHOipfrjaAUff
    hafma u / f
    HnffuA
    6070
    3 / (Hfsim, 2
    80
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE1218451B|1957-09-05|1966-06-08|Union Rheinische Braunkohlen|Process for the separation and recovery of heterocyclic compounds from high-temperature coal tar fractions|
    US3005826A|1958-11-17|1961-10-24|Union Oil Co|Organic nitrogen compound separation by selective adsorption|
    US3159632A|1960-11-25|1964-12-01|Dow Chemical Co|Repetitive process for the removal and/or recovery of amines from aqueous solutions|JPS6150945B2|1981-10-08|1986-11-06|Mitsui Toatsu Chemicals|
    US4769474A|1985-04-10|1988-09-06|Mitsui Toatsu Chemicals, Inc.|Process for purifying tryptophane|
    US4940830A|1988-09-26|1990-07-10|Uop|Rejective separation of para-xylene from xylene isomers and ethylbenzene with zeolites|
    US5174979A|1989-10-06|1992-12-29|Uop|Mixed ion-exchanged zeolites and processes for the use thereof in gas separations|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP14121579A|JPS6021587B2|1979-11-02|1979-11-02|
    JP1353280A|JPS6021588B2|1980-02-08|1980-02-08|
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