• 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:
    In a process for the selective hydrogenation of polyunsaturated compounds, by means of a catalyst system, the hydrogenation is carried out in gaseous phase in the presence of a catalyst of a metal of the eight group of the Periodical Table, partially deactivated by a deactivating system.
    公开号:SU749363A3
    申请号:SU762359448
    申请日:1976-05-20
    公开日:1980-07-15
    发明作者:Санфилиппо Доменико；Морелли Морелло
    申请人:Аник С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for producing cyclopentene or ethylene.
    A known method of producing cyclopentene by hydrogenation of cyclopentadiene 5 in the presence of a palladium catalyst on the axis of aluminum, additionally 1 containing 5-50 wt.% Calcium oxide or its mixture with a compound of copper or silver or zinc and / or iron. The process is carried out in the vapor phase at a temperature of 100-300 ° C [1].
    The closest in technical essence to the described method is the method of partial hydrogenation of unsaturated compounds containing at least two double bonds into monoolefin compounds at a temperature of 0-100 ° C in the presence of a solvent or diluent on a palladium catalyst poisoned by heavy ions Metal
    fishing, for example zinc, with the addition of a deactivator-ammonia to the reaction medium -...
    ka or amines. The cyclopenta-25 diene is hydrogenated according to this method in dibutyl ether as a solvent at room temperature and normal pressure in the presence of a suspended catalyst containing 0.5% palladium on a magnesium silicate support and partially poisoned with zinc ions, as well as deactivator-butyl amine L 2 J.
    The disadvantages of the described method include the frequency of operation, the problem of separation of reaction products due to the use of a suspended catalyst and obtaining insufficiently pure product with a content of ^ 0.7% cyclopentane.
    The aim of the invention is to increase the selectivity of the process.
    The goal is achieved by the described method of producing cyclopentene or ethylene by hydrogenation of cyclopentadiene or acetylene at a temperature of 65-220 ° C in the vapor phase in the presence of a palladium-zinc catalyst and a steam deactivator in an amount of 1-33 vol.% Or water vapor mixed with ammonia at their volume the ratio of 1: 0.4-40, or ammonium chloride in an amount of 1.1-1.18 weight,% introduced together with the catalyst.
    Palladium can be used on a carrier, for example, alumina, coal, calcium carbonate, barium sulfate, in the form of granules or in powder form, in a concentration of 0.01-5 wt.%, Preferably 0.01-0.5 wt.%.
    Zinc can be used in the form of chlorides, nitrates, sulfates, acetates, oxalates, citrates, hydrates, etc.
    The concentration of zinc on the catalyst varies widely from 0.01 to 30 wt.%, Preferably in the range of 0.1 to 5 wt.%.
    PRI me R 1. 100 weight.h. a catalyst containing 0.3% palladium on alumina in the form of granules is treated by boiling for 2 hours in 200 ml of a 15% aqueous solution of Ζη (СН Й COOlg · Н j0. After filtration and drying, the catalyst contains 2.24 wt.% Ζη. 75 g of the catalyst is loaded into the jacketed reactor (internal diameter 1.5 cm, height 38 cm). 30-50 standard l / h of H 2 and 27-55 standard l / h of 20 cyclopentadiene (CPP) are passed through the catalyst. barely.
    further results: H 2 / CPD 0.92 1,02 1,1 1,2 1.65Conversion% 80 '90 95 97.5 100 25 Selectivity,% 90 87 ... 84 81 35 thirty Exit, % 72 78.3 79.8 79 35At m e p 2. Similarly described 35 mu in the example 1 prepare kata 0
    lyser containing 0.94% Ζη.
    50 standard l / h of H 2 and 38-46 standard 40 l / h of cyclopentadiene are passed through the catalyst, then 37 standard l / h of the following results:
    . n 2 /
    CPD 1,081.15
    Conversion,% 9095
    Selectivity,% 93,591.5 ‘Yield,% 8487 get EG, 23 1.3 '45
    97.5 99.5 fifty 89.5 78.587.3 78
    Example 3. The dream catalyst of Example 2 is passed 50 standard l / h N 2 39-49 standard l / h cyclopentadiene, 40 standard l / h steam and 1 standard l / h
    ammonia and get the following results: 60 H 2 / 1,02 TsPD Kon- 1,08 1.15 1.27ver- 100this,% 95 97.5 99.5 65
    Selectivity,% 94 92 8675.3
    Yield ^ 89.3 89.7 85.675.3
    PRI me R 4. 100 g of a catalyst containing 0.3% Pd on ACO, in the form of granules, is boiled for 2 hours in 200 ml of an aqueous solution containing 5 wt.% Ζη (СН e С00) 2 -2Н 2 0 and 3 wt.% NH ^ Cl.
    After filtration and drying, the catalyst contains 0.9 wt.% Zinc and 1.1% ammonium salt (0.73% C).
    50 standard l / h of hydrogen and 2730 standard l / h of cyclopentadiene are passed through the catalyst and the following results are obtained:
    n 2 / JRCConver- 1.68 .1.76 1.84 this,% Selective- 95 97.5 99.8 nost,% you- 94.5 93 80 move% 89.7 90.6 79.8 Prim er 5. Through the catalyst an example 4 miss 50 standard-
    l / h of hydrogen, 27 standard l / h of CPD and 37 standard l / h of steam, while this provides 93% selectivity, 99.5% conversion and a yield of 92.5%.
    PRI me R 6. Through the catalyst of example 4, pass 50 standard l / h of hydrogen, 24-49 standard l / h of cyclopentadiene, 37 standard l / h of steam, 1.8 standard l / h of gaseous ammonia and get the following results :
    . H 2 / 1.02 1.05 1.06 1.08 1.15 2.04
    JRC
    Conversion,% 90 95 97.5 99.5 100 100
    Selectivity,% 98.9 98.5 98 97.4 97.2 93
    Yield,% 89 93.6 95.5 97 97.2 93
    Example 7. Through a catalyst containing 0.04% Pd on A1 2 Au and 1.1% Ζη, 50 standard l / h of ethylene containing 1% C 2 H 2 and various amounts of hydrogen are passed. The following results are obtained:
    H 2 /
    C a H 2 V 13 2D D2 23 33 9 93 10.5
    Temperature ° C
    121 121 121 65 65 150 121 150 120 s
    c 2 !, e h / mli 148 125 34 720 0 0 0 image (
    0D7 0.31 0.42 0.45 0.49 1.25 2.3 6 ( 4 8.7 95.
    Example 8. Through a catalyst 5 containing 0.04% Pd on AI ^ O ^ in the form of granules, and 1.17% Zn, 50 standard l / h of ethylene containing '1% C 2 H 2 , 0.8 standard l / h are passed couple; 2 standard l / h of gaseous ammonia and H 2 in various ratios. The following results are obtained:
    H 2 /
    C 9 P 9 1 1.1 1.2 1.4 2.8 2.9 9 9 9.,
    Temperature 15 ,
    C 120 120 120 150 63 63 63 125 15θ2Ο C 2 H 2 ppm 40 2 0 2 22 2 00 0
    C 2 H Z ,% 0.08 0.1 OD 5 0.4 029 0.38 0.47 6.35 7.6
    PRI me R 9 Through a catalyst 45 containing 0.04% Pd on Al ^ Oj, in the form of granules, and also 0.15% Zn and 1.18% NH4CI, 50 standard l / h of ethylene containing 1 were passed % C 2 H 2 . .
    0.8 standard l / h of steam, 2 standard l / h of gaseous ammonia and hydrogen in various ratios. The following results are obtained: 'n 2 /
    C 2 n 2 1.1 1.2 1.5 4.8 8.7 8.8 9
    Temperature, ° C 155 155 120 120 155 155 120 69% Н 2 ppm. 14921,400 0
    C 2 H 6 % 0.06 0.06 0.15-0.26 2.9 3.1.38
    权利要求:
    Claims (2)
    [1]
    (54) METHOD OF OBTAINING CYCLOPENTENE 1 -...--, l, ... ... .. The invention relates to the method of producing cyclopentene or ethylene. A known method of producing cyclopentene by hydrogenating cyclopentadiene in the presence of a palladium catalyst on an aluminum axis, additionally containing 6 to 5% by weight,% of calcium oxide or its mixture with a compound of copper or silver or zinc and / or iron. The process is carried out in the vapor phase at a temperature of SO-ZOO C 1. The closest in technical essence to the described method is the method of partial hydrogenation of unsaturated compounds containing at least two double bonds into monoolefinic compounds at a temperature in the presence of a solvent or diluent on a palladium catalyst poisoned by ions of heavy metals, for example zinc, with the addition of a deactivating amna or amines to the reaction medium. The cyclopentane diene is hydrated according to this method in a dibutyl ether as a solvent in rooms The temperature and normal pressure in the presence of a suspended catalyst, ETHYLENE containing 0.5% palladium on a magnesium silicate carrier and partly poisoned with zinc ions, and also a deactivator butylamine I. are disadvantageous. The problem of separation of the reaction products is application of suspended, catalyst, and obtaining an insufficiently pure product with a content of 0.7% of cyclopentane. The aim of the invention is to increase the selectivity of the process. This goal is achieved by the described method of producing cyclopentene or ethylene by hydrogenating cyclopentadiene or acetylene at a temperature of 65-220 ° C in the vapor phase in the presence of a palladium zinc catalyst and deactivator-baud steam in an amount of 1-33% or water vapor mixed with ammonia with their volume ratio of 1: 0.4-40, or ammonium chloride in the amount of 1.1-1.18 wt.%, introduced together with the catalyst. Palladium can be used on a carrier, for example, alumina, coal, carbonate, barium sulphate. In the form of granules or in powder form, in a concentration of 0.01-5 ve, preferably 0.01 to 0.5 wt.%. Zinc can be used in the form of chlorides, nitrates, sulphates, acetate roxapates, 1 of nitrates, hydrates, etc. The concentration of zinc on the catalyst varies widely from 0.01 to 30% by weight, preferably in the range of 0.1 to 5% by weight. % Example. 100 weight.h. A catalyst containing 0.3% palladium on alumina in the form of granules is treated by boiling for 2 hours in 200 ml of an aqueous solution of Zn (C – Hj HgO. After filtration and drying, the catalyst contains 2.24 weight Zn. 75 g of catalyst loaded into a jacketed reactor (internal diameter 1.5 cm, height 38 cm). 30-50 standard liters / h Hj and 27-55 standard liters / h cyclopentadiene (CPD) are passed through the catalyst. The following results are obtained: At / 0.92 1.02 1.1 1.2 1.6 CPD Converter, 5 100 si,% 80 90 Selectively-,% 90 87, st, Euhod,% 72 78.3 79.8 79 P r and meper 2. Similarly, described in example 1 is prepared for a catalyst containing 0.94% Zn. 50 standard, l / h H and 38-46 standard l / h cyclopentadiene are passed through the catalyst, then 37 standard l / h of steam and the following results are obtained: On /. the catalyst of example 2 passes 50 standard l / h Hj 39-49 standard l / h of cyclopentadiene, 40 standard l / h of steam and 1 standard l / h of gaseous ammonia and the following results are obtained: 1.02 1.08 1.15 1.2 Hj, / TsPD konver97, 5 99.5 100 si,% 95 nost,% Vy89, 7 85.6 course,% 89.3 PRI me R D. 100 g of catalyst, containing 0.3% Pd on AljO in the form of granules, boiled for 2 hours in 200 ml of aqueous solution thief soderzheschego 5 wt. Zn () - 2H20 11 3 wt.% After filtration and the day the catalyst contains 0.9 wt.% Zinc and 1.1% ammonium salt (0.73% s). 50 standard l / h of hydrogen and 2730 standard l / h of cyclopentadiene are passed through the catalyst and the following results are obtained:%, 94.5% Yield,% 89.7 Example 5. 30 standard are passed through the catalyst | FROM Example 4 l / h of hydrogen, 27 standard. l / h of CPD and 37 standard l / h of steam, while providing 93% selectivity, 99.5% conversion and yield of 92.5%. Example 6. 50 standard l / h of hydrogen, 24-49 standard l / h of cyclopentadiene, 37 standard l / h of steam, 1.8 standard l / h of gaseous ammonia are passed through the catalyst of example 4, and the following results are obtained:, Ng / 1 , 02 1.05 1.06 1.08 1.15 2.04 CPD Conversion,% 90 95 97.5 99.5 100 100 Selectivity,% 98.9 98.5 98 97.4 97.2 93 Exit, % 89 93.6 95.5 97 97.2 93. PRI me R 7. A catalyst containing 0.04% Pd on and 1.1% Zn is passed through 50 standard l / h of ethylene containing 1% and different amounts of hydrogen. The following results are obtained: Ng /. 1 2D2 b 9 9.7 10.5 Temperature, 121 121 121 65 65 150 121 150 120 ppm 148 12 5 34 7 7 0 O 00 Image 0.7 0.31 0.42 0.45 0.45 0.49 1.25 6 , 4 8.7 95 PRI me R 8. Through a catalyst containing 0.04% Pd on in the form of granules, and 1.17% Zn, 5 standard liters of ethylene are passed through, containing 1% of CgHgf 0.8 standard l / h of steam, 2 standard l / h of gaseous ammonia and H2 in various ratios. The following results are obtained: 2.9 9 9 9 CgHgl 1.1 1.2 1.4 1.4 2.1 C 120 120 120 150 63 63 63 125 1 ppm 40 2 O 000% 0.08 OD OD 5 0.4 0.38 0.47 6.35 EXAMPLE 9 Catalyst containing 0.04% Pd on, in the form of granules, and also 0.15% Zn and 1.18 NH4C1, is passed through 50 standard l / h ethylene containing 1% CgHg. 0.8 standard L / h of steam, 2 standard L / h of gaseous ammonia and hydrogen in various ratios. The following results are obtained: Ng / CgHg 1.1 1.2 1.54.88.78.89 with 155 155 120 62 155 120 69 ppm. 14921400O CgNb% 0.06 0.06 0.15-0.26 2.9 3.1.38 Claims of Invention The method of producing cyclopentene or ethylene by hydrogenating cyclopentane or acetylene in the presence of a pallcate zinc catalyst and deactivating agent at elevated temperatures is different from that to increase the selectivity of the process, water vapor is used in the amount of 1.-ЗЗоб.% or water vapor in a mixture with ammonia at a volume ratio of 1: 0.4-40, or ammonium chloride in the amount of 1.11, 18 weight. %, introduced together with the catalyst, and the process is carried out in pairs howl phase at a temperature of 65 220 ° C. Sources of information taken into account in the examination 1. GDR patent number 101384, cl. 120 19/01, publ. 1973.
    [2]
    2. The patent of the Federal Republic of Germany 1181700, cl. 12-25 pub. 1965 (prototype).
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    同族专利:
    公开号 | 公开日
    SE7605828L|1976-11-24|
    BE842104A|1976-11-22|
    DK152205C|1988-07-18|
    DD124970A5|1977-03-23|
    SE421785B|1982-02-01|
    NL173516C|1984-02-01|
    CA1061804A|1979-09-04|
    DE2622917A1|1976-11-25|
    JPS51143601A|1976-12-10|
    IT1038403B|1979-11-20|
    GB1545287A|1979-05-02|
    DK152205B|1988-02-08|
    AU1380276A|1977-11-17|
    US4112007A|1978-09-05|
    NO150198B|1984-05-28|
    DE2622917C2|1986-04-10|
    ZA762825B|1977-04-27|
    AU504280B2|1979-10-11|
    NO761734L|1976-11-24|
    FR2311767A1|1976-12-17|
    NO150198C|1984-09-05|
    JPS611406B2|1986-01-17|
    FR2311767B1|1979-10-12|
    DK226576A|1976-11-24|
    NL7605575A|1976-11-25|
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    BE564339A|1957-02-05|1900-01-01|
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    DE1181700B|1961-05-20|1964-11-19|Basf Ag|Process for the partial hydrogenation of cycloaliphatic compounds containing at least two olefinic double bonds to cycloaliphatic monoolefins|
    DE2025411A1|1970-05-25|1971-12-09|
    US3900526A|1972-05-02|1975-08-19|Phillips Petroleum Co|Selective removal of 1,2 polyenes and acetylenic compounds from conjugated-diene feed using a nickel, iron or cobalt arsenide catalyst|
    US3819734A|1972-05-05|1974-06-25|Goodyear Tire & Rubber|Hydrogenation process|
    US3862252A|1972-12-28|1975-01-21|Kanegafuchi Chemical Ind|Method of selective hydrogenation of cyclopentadiene|CA1091700A|1976-12-28|1980-12-16|John F. Van De Castle|Selective hydrogenation process|
    US4204081A|1978-08-30|1980-05-20|The Goodyear Tire & Rubber Company|Selective hydrogenation of cyclopentadiene to form cyclopentene|
    FR2553760B1|1983-10-25|1986-05-02|Inst Francais Du Petrole|PROCESS FOR SELECTIVE HYDROGENATION IN THE PRESENCE OF SOLVENT OF ACETYLENIC COMPOUNDS OF A BUTADIAN RICH C4 HYDROCARBON CUT|
    JPS636911U|1986-06-27|1988-01-18|
    JPH0720891B2|1987-03-06|1995-03-08|住友化学工業株式会社|Method for producing cyclopentene|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT23666/75A|IT1038403B|1975-05-23|1975-05-23|PROCEDURE OF SELECTIVE HYDROGENATION IN THE GASEOUS PHASE OF MULTI-UNSATURATED COMPOUNDS|
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