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  • 专利说明
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    • 专利摘要:
    1453267 Branched chain primary alcohols PRODUITS CHIMIQUES UGINE KUHLMANN 15 April 1975 [30 April 1974] 15478/75 Heading C2C A saturated primary alcohol with an alkyl branch on the second carbon atom is prepared by reacting in the presence of a copper-containing catalyst a mixture of hydrogen and carbon monoxide with an aldehyde containing the same number of carbon atoms as the alcohol produced, the aldehyde having been obtained by hydroformylation of an olefinic compound optionally followed by aldolization-crotonization; the aldehyde is in the liquid state and the molar ratio of hydrogen to carbon monoxide is between 1À6 : 1 and 2À2 : 1, and in the residual gas the molar ratio is between 1 : 1 and 1À5 : 1. The gas mixture used may be obtained by the oxidizing cracking of methane and the residual gas is suitable for use for the hydroformylation of olefins. In examples a Cu/Cr 2 O 3 /BaO catalyst is used at 50-70 bars pressure, 140-160‹ C.; isobutyraldehyde is converted to isobutanol, 2- ethylhexenal to 2-ethylhexanol, and a C 18 ethylenic aldehyde obtained by aldolizationcrotonization of 3,5,5-trimethylhexanal is converted to a saturated C 18 alcohol. In comparison examples n-butyraldehyde is converted to nbutanol and 3,5,5-trimethyl-hexanal to the corresponding alcohol, in both cases with the production of higher molecular weight byproducts.
    公开号:SU1060102A3
    申请号:SU752128747
    申请日:1975-04-29
    公开日:1983-12-07
    发明作者:Геан Огюст；Мерсье Серж
    申请人:Продюи Шимик Южин Кюльман (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a process for the production of primary alcohols with the exclusion of a second carbon atom and can be used in the preparation of alcohols from aldehydes obtained during the process of hydroformylation of the corresponding olefins. Primary alcohols with branching at the second carbon atom are widely used as solvents, plasticizers, etc. A method is known for producing primary alcohols with branching at the second carbon atom by hydrogenating the corresponding aldehydes obtained by hydroformylation of olefins with subsequent, if necessary, dimerization of hydrogen-containing gas at 140-160 ° C and pressure up to 5 MPa using a copper-containing catalyst-O. The disadvantage of this method is the use of hydrogenation as a hydrogenating agent. hydrogen-containing gas with a content of basic substance is not less than 85%, the preparation and transport .rovka which are associated with significant costs. The deficit in hydrogen-containing gas is especially noticeable recently in the petrochemical industry due to the rapid growth of hydroevizational processes. All this significantly complicates the process. The purpose of the invention is to simplify the process. The goal is achieved by the method of obtaining primary alcohols with branching at the second carbon atom by hydriroxyl in the liquid phase of the corresponding aldehyde obtained by hydroformylation of olefin followed by dimerization, if necessary, with hydrogen containing gas at 140–160 ° and elevated pressure using a copper-containing catalyst the quality of hydrogen-containing gas using a mixture containing hydrogen and carbon monoxide in a molar ratio of 1.8-2, 0: 1, the process is carried out at a pressure of 5-7 MPa to obtain by the introduction of a gas mixture containing hydrogen and carbon monoxide in a molar ratio of 1.0 to 1.12: 1, which is sent to the hydroformylation stage. After hydrogenation, the resulting residual gas of the above composition is directed directly to the hydroformylation of olefins. The aldehydes are hydrogenated in the liquid phase in the presence of, for example, a copper catalyst, since it is insensitive to carbon monoxide. All other hydrogenation catalysts that are insensitive to carbon monoxide can also be used. Copper catalysts may contain as fillers or promoters one or more other metals, with the exception of elements such as cobalt and nickel, which lead to catalyst poisoning due to the formation of metal carbonyls that dissolve in the reaction products. I Among these catalysts, Ad-based catchers are based on Cu and usually stabilized with barium oxide. The relative amounts of the various constituents that make up the catalytic composition can vary widely. In particular, Cu (Cr20) BaO catalysts containing 30–40% Cu, 50–60%, and 5–15% BaO are particularly suitable for the preparation of 2-ethylhexanol by hydrogenation in the liquid phase 2-ethylhexanal. On such catalysts, the hydrogenation satisfactorily takes place at 100-250 ° C and a pressure above 1 MPa, the best results were obtained at temperatures lying between 150-180 C and a pressure of 5-10 MPa. The method is particularly suitable for producing primary alcohols with alkyl branching — at the second carbon atom from aldehydes obtained by aldolization — crotonation of oxaline aldehydes, because under these conditions the synthesis gas used without pretreatment for hydrogenation is then directly used for oxosynthesis. All primary alcohols with alkyl branching at the second carbon atom can be obtained by this method, especially interesting results are obtained for the synthesis of 2-ethylhexanol-1, isobutanol, 2-methylpentanol-1, 2-propylheptanol-1, 2-propyl-5-methylhexanol- 1, respectively, from 2-ethylhexen-2-al-1, 2-G4-methylpropen-2-al-1, 2-methylpenthen-2-al-1, 2-propyl-5-hepten-2-al-1, 2- propyl-5-methylhexene-2-al -1. Example 1. In a tubular reactor with a diameter of 2.5 cm and 2.1 cm in height, thermostatted by a water jacket and containing 1 liter of Adkins catalyst with a weight composition of CulCr Oj) BaO 40 (50) 10 is treated by flowing in continuous mode at 160 ° C under pressure of 5 MPa 415 g / h 2-methylhexenal. For carrying out the hydrogenation, a stream of 500 l / h of the mixture of H and CO is introduced in a molar ratio of H2 / CO 2. The hydrogenated product is obtained in the following weight ratio,%: 2-Ethylhexanal 0.02 2-Ethylhexenol 0.08 2-Ethylhexanol 99 , 1 T yellow products 0.8. 353 liters of gas consisting of both CO and HI in a molar ratio of H ,, 11 used directly for oxosynthesis, in particular for the production of propylene by hydroforming, n-butanal, which is used to obtain 2-ethylhexenal by aldolization - crotonation. Example 2. In a reactor filled with a catalyst, as in measure 1, they are treated with continuous wailing at 140 ° C under a pressure of 5 MPa and 430 g / hr n-butanal. To carry out the hydrogenation, a 450 L / h mixture of CO and H is introduced. in a molar ratio of H2 / CO 2, the resulting hydrogenation product has the following weight composition,%: Small aldehyde 0.05 Dibutyl ether 0.05 Butanol.89.1 T Target products .0.8 Dissolved 353 liters of gas consisting from CO and H2 in a molar ratio of H2 / CO 1., 11, used directly for oxosynthesis, in particular for the preparation by the guide The reforming of propylene n-butanal, which is used to obtain 2-ethylhexenal by aldolization - crotonization. Example 3. In a reactor filled with a catalyst, as in the example. 1, is treated by swelling in continuous mode at 140 ° C under a pressure of 5 MPa 430 g / h of n-butanal. To carry out the hydrogenation, 450 l / h of a mixture of CO l Uj are introduced in a molar ratio. The resulting hydrogenation product has the following composition by weight,%: Molar aldehyde 0.05 I butyl ether 0.05 Butanol89.1 T Desired products 10.8 Withdrawal of 316 liters of gas consisting of CO and H2 in a molar ratio of H2 / CO 1.12. Example 4. In a reactor laden with a catalyst, as in Example 1, 3,5,5-trimethylhexanal is processed during continuous swelling at 140 ° C under a pressure of 5 MPa 426 g / h. For carrying out the hydrogenation, a stream of 235 l of a mixture of CO and Nu is introduced in a molar ratio of H2 / CO 2. The resulting hydrogenation product has the following weight composition.,%: 3,5,5-Trimethylhexanal0, 25 3,5,5-Trimethylhexanol 94 , 0 T yellow products 5.75 Vent 158 liters of gas consisting of CO and Hj in a molar ratio Hj / C0 l, 10. Example 5. In a reactor loaded with a catalyst, as in Example 1, is treated with a wail in continuous mode at 140 ° C. under a pressure of 5 MPa and 430 g / h of i-butanol. To conduct the hydrogenation, a 475 l / h mixture with CO and H2 is introduced in a molar ratio of 1.8. The resulting hydrogenation product has the following weight composition,%: Isobutanal, 0.05 Diisobutyl ether, 0.15 Isobutanol, 98.8 Target products 1.2 Withdrawal of 340 liters of gas consisting of CO and H2 in a molar ratio of H2 / CO 1. Example 6. In a reactor loaded with a catalyst, as in Example 1, the process is processed in a continuous mode at 160 ° C. under a pressure of 5 MPa 400 g / h of ethylene aldehyde Cjg prepared by aldolization - crotonization 3,5,5-trimethylhexanal. To carry out the hydrogenation, 225 l of a mixture of CO and in a molar ratio of H2 / CO 2 are introduced. The resulting hydrogenated product has the following weight composition,%: Ethylene Aldehyde C (80.05 Ethylene. CnnpTQg0.15 Saturated: alcohol C {899.2 Heavy products 0,6 Discharge of 158 liters of gas per hour, consisting of CO and HQ in a molar H2 / CO ratio of 1.1 p. Example 7. In a 2.3 l stainless steel autoclave equipped with a stirring system and heating system, load 100 g of 2-ethylhexanal and 20 g of catalyst. in the form of a powder having the following WEIGHT composition: CuCCr 0) BaO- . 40 (50) 10. A gas mixture of CO and Hg is introduced in a molar ratio under a pressure of 7 MPa, then the contents of the autoclave are heated to 120 ° C and the temperature is raised from 120 to 160 ° C for 3 hours. Then the autoclave is cooled to room temperature. Extract the processed product to separate
    catalyst by filtration. Hydrogenated product has the following weight composition,%
    2-Ethylhexanap 0.05 2-Ethylhexenap -0.15 2-Ethylgvoxanol 99.2 T Desirable Products 0.6 Example 8. The process is carried out according to the procedure described in Example 4, but replacing 20 g of catalyst Cu (Cr20) BAO with Cu catalyst / ZnO with a weight composition of 40% Cu, Zn 60%.
    Hydrogenated product has the following weight composition,%;
    2-These hexanal 0.05 2-EthylhexeneNal 0.15 2-Ethylhexanol 98.6 T yellow products 1.2 T kim way, the proposed method greatly simplifies the process for
    due to the possibility of using a non-deficient mixture of hydrogen and carbon monoxide (waste cracking processes j having a molar ratio of 1.8-2.0: 1 in the hydrogenation process. As a result of hydrogenation, it is possible to simultaneously obtain the target product (primary alcohols with branching from the second carbon atom) and lower the hydrogen content in the mixture to a ratio of 1.01, 12: 1, which exactly corresponds to the same value in the process of hydroformylation of olefins, where the ratio Hl: CO is strictly regulated.
    Such technical design of the process significantly simplifies it by involving unqualified raw materials in the scheme.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING PRIMARY ALCOHOLS WITH BRANCHING AT THE SECOND CARBON ATOM by hydrogenating the corresponding aldehyde in the liquid phase, obtained by hydroformylation of an olefin, followed by dimerization, if necessary, with a hydrogen-containing gas at 140-160 ° С and increased pressure using a copper-containing catalyst simplification of the process, as a hydrogen-containing gas using a mixture containing hydrogen and carbon monoxide in a molar ratio of 1.8 - 2.0: 1, the process is carried out at a pressure of 5-7 MPa s Acquiring a gas mixture containing hydrogen and carbon monoxide in a molar ratio of 1.0 - 1.12: 1, which is directed to the hydroformylation.
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    类似技术:
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    同族专利:
    公开号 | 公开日
    FR2269511A1|1975-11-28|
    FR2269511B1|1978-01-27|
    AR203790A1|1975-10-15|
    BR7502595A|1976-03-09|
    CA1052395A|1979-04-10|
    DE2519011A1|1975-11-06|
    IT1032763B|1979-06-20|
    GB1453267A|1976-10-20|
    DE2519011B2|1978-01-19|
    NL7505089A|1975-11-03|
    AU8056875A|1976-11-04|
    ATA323775A|1976-12-15|
    DE2519011C3|1983-03-24|
    ES437215A1|1977-01-16|
    JPS5331847B2|1978-09-05|
    US4049725A|1977-09-20|
    BE826894A|1975-07-16|
    JPS5129406A|1976-03-12|
    AT338221B|1977-08-10|
    引用文献:
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    US2137407A|1931-05-11|1938-11-22|Du Pont|Catalytic hydrogenation process|
    US2694091A|1949-09-12|1954-11-09|Ici Ltd|Oxo process using mixture of alkenes and dienes|
    US2614107A|1949-11-01|1952-10-14|Wender Irving|Process for the reduction of carbonyl compounds|
    US2695315A|1950-10-07|1954-11-23|Standard Oil Dev Co|Synthesis of oxygenated organic compounds|
    US2670378A|1951-03-12|1954-02-23|Stanolind Oil & Gas Co|Method for converting oxygenated organic chemicals in hydrocarbon synthesis|
    US3102150A|1960-02-19|1963-08-27|Exxon Research Engineering Co|Process for hydrogenating carbonyl compounds|
    US3341610A|1961-04-24|1967-09-12|Quaker Oats Co|Hydrogenation of alpha, betaunsaturated aldehydes|
    US3647842A|1969-03-20|1972-03-07|Chevron Res|Stabilization of cobalt carbonyl compounds by oxygen-dentated ligands|
    DE1935900C3|1969-07-15|1975-03-13|Chemische Werke Huels Ag, 4370 Marl|Process for the removal of aldehydes and ketones from gas streams containing carbon monoxide|DE2840168A1|1978-09-15|1980-03-27|Basf Ag|METHOD FOR PRODUCING ALDEHYDES|
    DE3021744A1|1980-06-10|1981-12-17|Klavdija A. Alekseeva|2-Ethyl:hexanol prodn. from 2-ethyl-hexenal - by hydrogenation over zinc, copper and chromium contg. catalyst |
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    WO2005058782A1|2003-12-18|2005-06-30|Exxonmobil Chemical Patents Inc.|Improvements in or relating to hydrogenation|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7414962A|FR2269511B1|1974-04-30|1974-04-30|
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