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  • 专利说明
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  • 类似技术
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    • 专利摘要:
    An improvement in the process for the continuous manufacture of an aldehyde by reaction of an olefin with carbon monoxide and hydrogen in the presence of a rhodium catalyst at an elevated temperature and pressure followed by distillative separation of the non-converted feedstocks and low boiling components of the reaction mixture, the improvement residing in employing a carbon monoxide/hydrogen mixture containing 2-20 ppm sulfur and recycling residual rhodium compounds, both dissolved and suspended in the distillation residue, to the reaction zone.
    公开号:SU1017166A3
    申请号:SU782648754
    申请日:1978-08-15
    公开日:1983-05-07
    发明作者:Бекстен Лудгер；Корнильс Бой；Хан Гейнц-Дитер；Туммес Ганс
    申请人:Рурхеми Аг (Фирма)；
    IPC主号:
    专利说明:

    about:
    ABOUT)
    This invention relates to a process for the preparation of aliphatic aldehyde C by catalytic hydroformylation of olefin Cd.
    Methods are known for producing aldehydes by hydroformylation of olefins using a cobalt-containing catalyst in the presence of sulfur, which acts as a reaction initiator or catalyst promoter.
    . According to the first of the known methods, the process of hydroformylation of the olefin is carried out in the presence of sulfur /, taken in an amount of 0.05-10% by weight of cobalt in the catalyst. In terms of a mixture of carbon monoxide and hydrogen, the amount of sulfur is at least 0.004% by weight. In this case, sulfur plays the role of a reaction initiator, as evidenced by comparing the results of two experiments described in the example. The first experiment was carried out at 165-171s and a pressure of 243 kg / cm for 14 hours in the absence of sulfur. In this case, the reagents do not react. The second experiment was carried out at a temperature of about 243 kg / cm and for 4 hours in the presence of sulfur, taken in an amount of 2.7% by weight of cobalt (or 0.2% by weight mixtures of carbon monoxide and hydrogen) .. In this case, the reactants enter into the reaction l.
    According to the second method, sulfur, used as a catalyst component in an amount of 33.3% by weight of cobalt (Example 1), which corresponds to at least 24% by weight of a mixture of carbon monoxide and hydrogen, serves to increase the yield of aldehyde 2 .
    When carrying out the process in the presence of a rhodium-containing catalyst, the sulfur contained in the components of the reacting compounds poisoned the catalyst. Therefore, thorough purification of the olefin and synthesis gas from sulfur impurities 3J is necessary.
    The closest to the proposed technical essence and the achieved effect is a method of obtaining aliphatic aldehyde C by reacting isobutylene with carbon monoxide and hydrogen at 50-200 ° C under a pressure of 50-1000 atm in the presence of not more than 0.00002% by weight of a mixture of carbon monoxide and hydrogen sulfur on the rhodium-containing catalyst, separating the reaction mixture by distillation to the head product containing the desired product and the bottom product containing the catalyst, and recycling the bottom product to the t4 reaction.
    The disadvantage of this method is the loss of catalyst caused by deposition on the walls of the reactor, which complicates the process.
    In addition, from used re. agents must first carefully remove sulfur.
    The purpose of the invention is to simplify the process.
    5 The goal is achieved by the 4TocorjiacHo method of producing aliphatic aldehyde C by reacting isobutylene with carbon monoxide and hydrogen at a pressure of 150 atm in the presence of sulfur on a rhodium-containing catalyst, separating the reaction mixture by distillation into a head product containing the desired product and a bottom product 5 containing catalyst , and recycling the bottom product, the process is carried out in the presence of 0.0002-0.002%; sulfur by weight of a mixture of carbon monoxide and hydrogen.
    Simplification of the process is achieved by reducing the deposition of rhodium on the walls of the reactor and, accordingly, reducing the amount of catalyst introduced further into the process.
    Example 1. 143 kg of diisobutene, 8 kg of circulating catalyst, 0.1 kg of fresh catalyst (solution of Rh-2-ethylhexanoate in toluene), 0 containing 0.1 g of rhodium, are fed into the high-pressure reactor with a capacity of 580 liters hourly. 70 nm synthetic gas (the ratio of carbon monoxide and hydrogen is 1: 1, the sulfur content is 0.00015% in the form of HLS and 0.0014% in the form of COS).
    5 The circulating catalyst is a catalyst which is separated from the oxosynthesis product obtained in this example.
    The circulating catalyst contains 0.57 g of rhodium; 2.7 kg Cd - al0 dehyd; 0.5 kg C, - alcohol and 4.79943 kg of condensed oil.
    The reaction is carried out at and at a pressure of 150 atm with vigorous stirring of the reaction mixture 5 with feed syngas. Liquid reaction products and excess gas are withdrawn from the top of the reactor and, after cooling, are separated in a high pressure separator into liquid and gaseous products.
    Get 176 kg of a liquid product of the following composition,%:
    Isooctane2,1
    Diisobutylene 25.8 CQ-aldehyde 67.4 C -alcohol1.5
    Condensed Oil 3.2 After removal of pressure, the product is separated by distillation. Under a pressure of 80 NB Hg. at a temperature of bottom 0 of the column 125 ° C per a head product and a bottom product containing catalyst. At the same time, 167.1 kg of the head product and 8.9 kg of the bottom product of the following composition BOB,% are received every hour:
    Head
    VAT product
    Isooctane 2,2Diisobuti-. flax 27,2 C - aldehyde 69,3 30 C, - alcohol 1,35,6
    Condensed
    oil 164.4
    In this case, the conversion of E of diisobutylene is 68.4% in terms of starting diisobutylene, and the yield of Cp-aldehyde and C is 95.1% of alcohol, calculated on the reacted diisobutylene.
    The bottom product with a content of 0.55 g of rhodium after the addition of O, 1 g of rhodium in the form of a solution of Rh-2 ethyl hexanoate in toluene is again used for synthesis.
    After 100 h, get 176 kg of the liquid product composition, wt.%: 1
    Isooctane2,3
    Diisobutylene 26.2 Aldehyde CQ 66.6 Alcohol Cd1.7
    Condensed oil 3.2 After separation by distillation, 166.9 kg of the head product and 9.1 kg of the bottom product are obtained, the following compositions, wt.%:
    Vat
    Head product product
    Isooctane 2,4
    Diisobutylene 27.5
    Aldehyde 68.9, 30.3
    Alcohol With 1,2 1,2,4
    Condensed
    butter- . 62.3
    In this case, the conversion of diisobutylene is 68% in terms of starting diisobutylene, and the yield of aldehyde C and alcohol Cd is 94.8% in terms of reacted diisobutylene.
    8 kg of bottom product with a content of 0.57 g of rhodium after the addition of 0.1 g of rhodium in the form of a solution of Rh-2-ethylhexanoate in toluene dreams is used for synthesis.

    After 200 hours, 176 liquid products of the following composition are obtained, & eu.%:
    Isooctane2,4
    Diisobutylene / 25.1. .
    Aldehyde C, 67.1
    Alcohol C, 2.0
    Condensed butter 3,4
    After separation by distillation, 166.8 kg of the head product and 9.2 kg of the bottom product of the following composition are obtained, wt.%:
    Head
    VAT product
    Isooctane 2,5 Diisobutylene 27.4
    Aldehyde C 68.1 29.8 Alcohol Cd 2.0 6.9 Condensed.
    oil 63,3
    In this case, the conversion of dinzobutylene is 69% in terms of the starting diisobutylene, and the yield of aldehyde C | j and alcohol of Su is 94.8% in terms of the reacted diisobutylene.
    8 kg of the bottom product with a content of 0.58 g of rhodium after the addition of 0.1 g of rhodium in the form of a solution of Rh-2-ethylhexanoate are used again for synthesis.
     After 300 hours, 176 kg of liquid product of the composition, wt.% Are obtained:
    Isooctane2,4,
    Diy obulen 26.1 Aldehyde Cp66.1
    Alcohol with 2.1
    Condensed oil 3.3. After separation by distillation, 166.6 kg of the head product and 9.4 kg of the bottom product of the following compositions are obtained, wt.%:
    Head Cubic .product product
    Isooctane. 2.5 Diisobutylene 27.7. Aldehyde CL 68.1 29.2
    Alcohol C 1.7 7.1
    Condensed
    oil - 63,7
    The conversion of diisobutylene is 67.85% based on the starting diisobutylene, and the yield of aldehyde C and alcohol C is 94.6% based on the reacted diisobutylene.
    8 kg of bottom product with a content of 0.58 g of rhodium after the addition of 0.1 g of rhodium in the form of a solution of Rh-2-ethylhexoate in toluene is again used for synthesis.
    EXAMPLE 2 Example 1 is repeated with the difference that the synthesis gas supplied to the reaction contains 0.0002% sulfur as H and COS in a ratio of 1:10. The conversion of diisobutylene averages 63.5%, and the average yield of aldehyde and alcohol is 94%.
    Example 3. Example 1 is repeated. The difference is that
    - on the reaction, the synthesis gas contains 0.002% of sulfur in the form and COS in a ratio of 1: 2. The conversion of diisobutylene is on average 69.8%, and the average yield of aldehyde and alcohol is 95.4%.
    Example 4 (comparative; Example 1 is repeated, with the difference that 143 kg of dinzobutene is fed every hour to the synthesis; 9 kg of the circulating catalyst, 0.2 kg of fresh catalyst containing 0.18 g of rhodium in the form of Rh-2-ethylhexanoate, 70 nm of synthesis gas (the ratio of carbon monoxide and hydrogen is 1: 1, the sulfur content in the form is 0.0000084 and 0.00001% in the form of COS). The circulating catalyst consists of 2.6 kg of " aldehyde, 0.5 C-spirits and 5.9 kg of condensed oil and contains 0.6 g of rhodi.
    Get 177 kg of a liquid product of the following composition,%:
    Isooctane2,1
    Dkizobutylene. 26.2 Cf-aldehyde 66.4. C9-alcohol1,7
    Condensed butter. 3.6 After separation by distillation, 167.6 kg / h of the head product and 9.4 kg / h of the cubic product of the following composition are obtained,%:
    Vat
    Head product product
    2.2
    27.7 68.6
    28.7
    C-spyrt - 1.5 5.3
    Condensed
    butter . - 64.0,
    The conversion of diisobutylene is 67.6% in terms of starting diisobutylene, and the yield of C9-aldehyde and C-alcohol is 95% in terms of reacted; and 1 of 6 butyl.
    The bottom product with a content of 0.56 g. Rodi after the addition of 0.2 g 0 rhodium in the form of a solution of Rh-2-ethylenehexanoate in toluene is again used for synthesis.
    To achieve an average degree of diisobutylene conversion of 67% and an average 5% yield of the target products 94%, 0.2 g of fresh rodi is added hourly over 300 hours.
    Example 5 (comparative) (sulfur in an amount of less than 0.0002%). Example 1 is repeated, with the difference that the synthesis gas supplied to the reaction contains 0.0001% of sulfur in the form and COS in a ratio of 1:10. At the same time, the conversion of diisobutylene is on average 53.6%.
    Example 6 (comparative) (sulfur in the amount of more than 0,002%). Example 1 is repeated, with the difference that the synthesis gas supplied to the reaction contains 0.003% sulfur as
     and COS at a ratio of 1:10. With; This conversion of diisobutylene is on average 65%.
    权利要求:
    Claims (1)
    [1]
    Process for the preparation of aliphatic aldehydes C 9 by reacting isobutylene oxide of carbon and hydrogen at 150 e C and a pressure of 150 atm in the presence of sulfur on the rhodium-containing catalyst, the separation by distillation of the reaction mixture into an overhead product containing the desired product and a bottoms product containing the catalyst, and recycling the bottoms product, characterized in that, in order to simplify the process, it is carried out in the presence of 0.0002-0.002% sulfur from the weight of the mixture of carbon monoxide and hydrogen.
    8 | cl with
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    同族专利:
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    引用文献:
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    JPS5822453B2|1974-07-15|1983-05-09|Mitsubishi Chem Ind|
    US4248802A|1975-06-20|1981-02-03|Rhone-Poulenc Industries|Catalytic hydroformylation of olefins|US4374278A|1980-02-28|1983-02-15|Union Carbide Corporation|Hydroformylation catalyst reactivation|
    US4324695A|1980-11-17|1982-04-13|National Distillers & Chemical Corp.|Catalyst compositions of transition metal carbonyl complexes intercalcated with lamellar materials|
    DE3114147A1|1981-04-08|1982-10-28|Basf Ag, 6700 Ludwigshafen|METHOD FOR OBTAINING ALDEHYDES|
    US5082977A|1990-02-15|1992-01-21|University Of Akron|Aldehydes by olefin hydroformylation|
    DE102012013968A1|2012-07-13|2014-04-03|Oxea Gmbh|Carboxylic acid ester of isononanoic acid starting from 2-ethylhexanol, process for their preparation and their use|
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    法律状态:
    优先权:
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    DE2737633A|DE2737633C2|1977-08-20|1977-08-20|Process for the production of aldehydes|
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