• 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:
    Metal carbonyl clusters occluded in zeolites are prepared, to be used as catalyst in certain special reactions such as hydroformylation of diene hydrocarbons. Rhodium complexes are immobilized in certain zeolites and the catalyst thus obtained can be used as a heterogeneous catalyst.
    公开号:SU953971A3
    申请号:SU782574402
    申请日:1978-01-31
    公开日:1982-08-23
    发明作者:Мантовани Элвио；Палладино Николя；Заноби Антони
    申请人:Снампрогетти С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    (B) METHOD OF PREPARATION FOR HYDROPHOX OF HEXEN OR I This invention relates to methods for the preparation of catalysts for the hydration, reforming of olefins and dienes, in particular hexene or hexadiene. Closest to the present invention is a method for preparing a catalyst for hydroformylation of olefins, consisting in treating a carrier, for example Ab20e SiO (j or silica-alumina, with a rhodium-containing compound, followed by reacting with carbon monoxide to form different rhodium carbonyls. on the surface of the carrier, without using the internal spaces of l. The disadvantages of the known method of preparation of the catalyst include the presence of complex Catalyst recovery operations, in addition, the catalyst obtained in a known manner is dispersed in the reaction medium and contaminates the reaction products. SADIENE CATALYST OPERATOR The purpose of the invention is to simplify the method of preparation of the catalyst. or hexadiene, which consists in treating the support, use NaY zeolite as a support, a rhodium-containing compound, which uses a set of kc pL (LiH), and carbonylation of which are a mixture of carbon monoxide and hydrogen in a ratio of 1: 1. The use of zeolite as a carrier results in a catalyst with increased activity and selectivity. The essence of the present process is as follows. NaY-type zeolite is treated with the complex compound fPh (NH,) (The thus subjected to ion exchange the zeolite is treated with a mixture of carbon monoxide and hydrogen. Example 1.3 g of the NaY-type zeolite is treated with a solution containing 80 mg of Ph (NHa) CC complex in 50 ml of water. 48 hours ion exchange is completed. The ion exchanged zeolite is washed with water until there are no chlorine ions and dried. The presence of a rhodium-amine complex inside the zeolite is confirmed by the identification of the infrared spectrum of the 1322 cm band, which is characteristic of such a complex. Thus exchanged zeolite is then treated in an autoclave for 48 hours at 130 ° C using a mixture of CO and H (1: 1) under a pressure of 80 kg / cm, as a result of which a product is obtained that is intensely colored in red and the analysis of which shows 1% Rhodi. The infrared spectrum showed a band at 1322 cm which is a characteristic amine component, and the appearance of intense polo at 2095, 2080, 2060 and 1/65 cm. These bands indicate the presence of coded carbon monoxide and suggest the formation of carbonyl clusters in the zeolite. The catalyst thus prepared is used in the hydroformylation of hexene-1. 71 mg of catalyst (7 per 10 mg-atoms of rhodium) and 1 ml of hexene -1 in 5 ml of hexene are placed in an autoclave having a volume of
    Table 1 1 200 ml, which is loaded with a mixture of CO and H (1: 1) under a pressure of 80 kg / cm and brought to a temperature of 8 ° C. Through . At 8 hours, the temperature in the autoclave was adjusted to room temperature, and the reaction mixture was subjected to gas chromatography. The conversion of hexene -1 to aldehyde is about 98, of which 5C is heptanal, 1-methylhexanal and 8 2-ethylpentanal. Other reaction products are present in an amount of less than%. Example 2. A catalyst similarly to 1 is removed by filtration of the reaction mixture and reused under the same conditions in 8 consecutive hydroformylation tests (Tables 1 and 2). The eighth test, which gives the same results with respect to the degrees of conversion and composition of the reaction mixture, which are indicated in the example above, shows a high stability of the catalyst, whose properties remain unchanged even after a series of repeated catalytic cycles. f i Catalyst losses during the reaction are extremely low, and in fact the average content of rhodium in the reaction mixture, according to atomic absorption analysis, is about 3 parts per million.
    Note. Pressure 80 kg / cm (1CO + IH)), 5 ml of hexane: 1 ml of hexane - 1 mg of catalyst (7 10 mgatoms of rhodium). n / i is the ratio of normal aldehyde to isoaldehyde. Notes Example 3.71 milligrams of catalyst (7-10 mg of rhodium atoms) prepared according to example 1, 1 ml of 1,5-hexadiene in 5 ml of benzene is placed in a 200-ml autoclave, which is charged at a pressure of 80 kg / cm with a mixture of CO and H (1: 1) and brought to a temperature of 80 ° C. After 8 h, the temperature in the autoclave is adjusted again to room and the reaction mixture is subjected to gas chromatographic analysis. Conversion of 1.5 hexadiene is higher than 80C which is monoaldehyde and 51% isomer of dialdehyde C2%, 8%, (% and 3%, respectively).
    权利要求:
    Claims (1)
    [1]
    - 1. e. Temperature BS, 5 ml hexane: 1 ml hexane 71 mg of catalyst (7 10 O mg-atoms of rhodium) p / I ratio of normal aldehyde to isoaldehyde. DETAILED DESCRIPTION OF THE INVENTION Method for preparing a catalyst for hydroformylation of hexene or hexadiene, including treating the support with a rhodium-containing compound and carbonylation, characterized in that, in order to simplify the process, use is made of a NaY-type zeolite as a support; a mixture of carbon monoxide and hydrogen in a 1: 1 ratio. Sources of information taken into account in the examination 1. US Patent Vf 28802 1, cl. 260-60, published. 1959 (prototype).
    类似技术:
    公开号 | 公开日 | 专利标题
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    Schultz et al.1966|Olefin dimerization over cobalt-oxide-on-carbon catalysts: I. Propylene dimerization
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    Whyman1982|Industrial aspects of cluster chemistry
    Taarit et al.1980|Catalytic Reactions Induced by Transition Metal Complexes Solvated in Zeolite Matrices: Oxidation, Carbonylation and Related Reactions
    Brookhart et al.1973|Isomerization of 1, 3, 5-cyclooctatrieneiron tricarbonyl to bicyclo [4.2. 0] octa-2, 4,-dieneiron tricarbonyl
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    同族专利:
    公开号 | 公开日
    AU516336B2|1981-05-28|
    CA1107266A|1981-08-18|
    ZA78614B|1979-09-26|
    DE2804307B2|1979-06-13|
    ATA66178A|1980-03-15|
    AU3260178A|1979-07-26|
    DK45078A|1978-08-02|
    IT1074824B|1985-04-20|
    AT359046B|1980-10-10|
    US4334101A|1982-06-08|
    CH634020A5|1983-01-14|
    GB1570258A|1980-06-25|
    BE863548A|1978-08-01|
    SE7801215L|1978-08-02|
    DE2804307A1|1978-08-03|
    FR2378563A1|1978-08-25|
    JPS5396999A|1978-08-24|
    FR2378563B1|1980-05-16|
    LU78967A1|1978-06-21|
    NL7801155A|1978-08-03|
    SE431515B|1984-02-13|
    US4199478A|1980-04-22|
    DE2804307C3|1980-03-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3236761A|1951-01-28|1966-02-22|Union Carbide Corp|Hydrocarbon conversion process and catalyst|
    NL243444A|1958-09-24|
    FR1233890A|1958-09-24|1960-10-12|Union Carbide Corp|Process for preparing zeolite molecular sieves loaded with a metal|
    US3013987A|1958-09-24|1961-12-19|Union Carbide Corp|Metal loading of molecular sieves|
    FR1243036A|1958-09-24|1960-10-07|Union Carbide Corp|Process for preparing zeolite molecular sieves loaded with a metal|
    US3013990A|1961-09-11|1961-12-19|Union Carbide Corp|Iron group metal catalyst|
    US3201356A|1961-09-27|1965-08-17|Exxon Research Engineering Co|Molecular sieve catalyst activation process|
    JPS49822B1|1970-04-15|1974-01-10|
    US3940447A|1970-04-27|1976-02-24|Atlantic Richfield Company|Process for hydroformylation of olefin hydrocarbons|
    US3954883A|1970-07-23|1976-05-04|Mobil Oil Corporation|Catalytic polystep reactions|
    US3980583A|1974-02-19|1976-09-14|Mobil Oil Corporation|Complexed metals bonded to inorganic oxides|
    US4070403A|1975-07-21|1978-01-24|Uop Inc.|Catalytic hydroformylation process|
    US4197414A|1977-06-06|1980-04-08|The Dow Chemical Company|Amine-resin supported rhodium-cobalt bimetallic clusters as novel hydroformylation catalysts|US4324695A|1980-11-17|1982-04-13|National Distillers & Chemical Corp.|Catalyst compositions of transition metal carbonyl complexes intercalcated with lamellar materials|
    US4552855A|1982-12-30|1985-11-12|Ozin Geoffrey A|Metal zeolite catalyst preparation|
    NZ206702A|1982-12-30|1986-06-11|G A Ozin|Zeolite-metal catalysts containing essentially zero-valent clusters of metal atoms|
    US4847229A|1983-11-14|1989-07-11|The Dow Chemical Company|Process for hydroformylation of unsaturated compounds using iron carbonyl catalysts|
    US4782188A|1983-11-14|1988-11-01|The Dow Chemical Company|Process for hydroformylation of unsaturated compounds using iron carbonyl catalysts|
    US4994427A|1988-11-28|1991-02-19|Virginia Tech Intellectual Properties, Inc.|Supported aqueous phase organometallic catalyst useful for hydroformylation and other reactions, and a method for its preparation|
    US4947003A|1988-11-28|1990-08-07|Virginia Tech Intellectual Properties, Inc.|Process for the hydroformulation of olefinically unsaturated organic reactants using a supported aqueous phase catalyst|
    US5099047A|1989-11-17|1992-03-24|Mitsubishi Kasei Corporation|Method for recovering a group viii metal solid complex and hydroformylation method|
    IT1237530B|1989-12-12|1993-06-08|Eniricerche Spa|PROCEDURE FOR THE DIRECT SYNTHESIS OF ALCOHOLS FROM OLEFINS, CARBON OXIDES AND HYDROGEN, PROMOTED BY A SUPPORTED RHODIUM CATALYST|
    DK169717B1|1989-12-22|1995-01-23|Topsoe Haldor As|Crystalline aluminosilicate modified with metal sulfide, method of preparation and use thereof|
    US5167942A|1990-11-21|1992-12-01|Board Of Regents, The University Of Texas System|Methods for the preparation of molecular sieves, including zeolites, using metal chelate complexes|
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    US20140121427A1|2012-10-29|2014-05-01|The Regents Of The University Of California|Methods of Activating Metal Complexes for Catalysts|
    CN105498759B|2015-12-01|2018-03-16|中国科学院大连化学物理研究所|A kind of acetylene ring trimerization prepares benzene high performance catalyst and its preparation method and application|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT19833/77A|IT1074824B|1977-02-01|1977-02-01|METAL-CARBONY CLUSTERS PREPARATION METHOD IMMOBILIZED IN ZEOLITES AND THEIR USE AS HETEROGENEOUS CATALYSTS|
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