• 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:
    Process for removing alkyl substituted phosphine from a hydroformylation medium and enhancing the rhodium complex catalyst contained therein via an oxygenation treatment.
    公开号:SU1757458A3
    申请号:SU813336900
    申请日:1981-09-23
    公开日:1992-08-23
    发明作者:Биллиг Эрнст；Брюс Стэнтон Дэвид
    申请人:Юнион Карбид Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    catalysts for the reaction of hydroformylation, as well as in the presence of free triarylphosphine 1.
    It is also known that rhodium complexes that serve as catalysts lose their activity (i.e., become partially deactivated) with prolonged use, therefore, the method of reactivating these partially deactivated complexes is of great importance for this industry due to the high cost of delivery. . Although it is difficult to establish all the causes of this loss of activity, it is obvious that with a large-scale hydroformylation reaction, the loss of activity is at least partially due to the presence of alkyl-substituted phosphines in the reaction medium in which the hydroformylation reaction is carried out. For example, the presence of alkyl diarylphosphine in a rhodium complex, which serves as a catalyst for the reaction of propylene hydroformylation, inhibits catalyst productivity, i.e. reduces the rate of formation of the desired product, aldehyde. When the triarylphosphine ligand is used in hydroformylation of alpha-olefins, zlkylarylphosphine forms in situ, and its alkyl group is usually derived from alpha-olefin that underwent hydroformylation, and its aromatic group is equivalent to the aromatic group that forms part of the triarylphosphine. In the continuous process of hydroformylation of alpha-olefins in the presence of a triarylphosphine ligand, aldehydes are obtained from it, and the continuous reproduction of such alkyl-substituted phosphines can in some cases lead to a decrease in the reaction rate and catalyst activity based on rhodium complexes due to the affinity of such alkyl-substituted phosphines with respect to catalyst.
    There is also known a method of hydroformylation of olefins (including propylene), which uses the stabilization effect that alkyl diarylphosphine has on the catalyst based on the rhodm in these hydroformylation reactions under more severe conditions of the reaction to compensate for the loss of productivity for the catalyst after by maintaining the catalytic activity as a result of an increase in the stability of the catalyst in the presence of the indicated alkyl diarylphosphines 2
    There is also known a method of hydroformylation of olefins, which includes maintaining or increasing the activity of rhodium-based catalysts for hydroformylation reaction by washing the entire volume or part of its liquid medium containing the catalyst with an aqueous solution, for example an aqueous alkali solution, to remove acid by-products,
    For example, carboxylic acids formed in the process of carrying out a hydroformylation reaction as a result of aldehyde oxidation, which may occur due to the penetration of oxygen into the gas flow of the reagents 3.
    A method of hydroformylation is also known, which includes maintaining or increasing the catalytic activity of a catalyst based on rhodium for the reaction
    0 hydroformylation as a result of removal of the aldehyde from the overclocked mixture of reaction products containing the catalyst, followed by treatment of all the liquid medium containing the catalyst, or part of it
    5 With oxygen in the process of catalyst recycling to the hydroformylation reaction. 4 There is also known a method for regenerating rhodium catalysts for the hydrophore reaction of milirovanie, including the steps of removing the entire inactive catalyst or part of it from the hydroformylation reaction, adjusting the aldehyde content so that
    5 at least 1 mol of aldehyde per 1 mol of rhodium and ligand (for example, triphenylphosphine) and the treatment of the catalyst containing the aldehyde with oxygen or a gas containing oxygen at a temperature
    0 lower aldehyde boiling point, as well as removal of the total amount of solid products formed during the oxidation process, and bringing the ratio of ligand and rhodium to the required
    5 carrying out the hydroformylation reaction 5.
    There is also known a method of hydroformylation, according to which the productivity of the process is maintained at the desired
    0 as a result of the supply of sufficient oxygen and the hydroformylation reaction is carried out in a homogeneous liquid reaction mixture, which maintains or increases the activity of the catalyst based on phodium 6. The known methods provide for the reactivation in a special container that is different the reaction of hydroformylation, and the alkyl-substituted phosphine, which is present in the reaction medium, shows a harmful effect. Closest to the proposed is a method of hydroformylation of olefins (including propylene) with carbon monoxide and hydrogen at 80–200 ° C and a pressure of 80–600 atm in the presence of a catalyst which is a mixture of rhodium with triphenylphosphine to form a reaction mass containing oil aldehyde , high-boiling byproducts of oil aldehyde compensation, propyl diphenylophosphine triphenylphosphine and the rest containing the complex rhodium catalyst triphenylphosphine oxide and high-boiling organic components batyvayut oxygen or oxygen-holding gas at 40-60 ° C for 4 h
    7
    The disadvantage of this cophenol is that up to 50% of aldehyde and up to 25% of triarylphosphine are lost during the treatment, which leads to a decrease in the activity of the catalyst. In addition, acids are obtained with a yield of up to 60-80%, which requires an additional stage of their separation
    The aim of the invention is to increase the activity of the catalyst.
    This goal is achieved by the method of producing oil aldehyde by hydroformylation of propylene with carbon monoxide and hydrogen in the presence of a catalyst that is a mixture of born with triphenylphosphine, with the formation of a reaction mass containing oil aldehyde, high boiling point by-products of oil aldehyde condensation, propyldiphenylphosphine, propyl dihydrophenylphosphine, propyl dihydrophenylphosphine triphenylphosphine and the rest, containing a complex rhodium catalyst, triphenylphosphine oxide and high-boiling organic components, followed by After the hydroformylation process has been performed, the hydroformylation reaction is stopped and the reaction mass is treated with oxygen-containing gas under conditions different from hydroformylation conditions at 54-70 ° C and a partial pressure of oxygen of 10 - Yatm, and the treatment is carried out This means that 63-94% by weight of propyldiphenylphosphine is converted to its corresponding oxide compound and 11-23% by weight of triphenylphosphine is converted to triphenylphosphine oxide.
    If more than one reactor is used, then there is no need to stop the reaction in each of the reactors;
    conduct a similar shutdown only in the reactor in which the reaction medium to be treated is contained. If desired, the whole reaction medium to be treated can be introduced from the reactor in which the reaction is carried out to another reactor, followed by treatment of all or part of the reaction mixture The reactor under the desired conditions. The introduction of such an additional stage makes it possible to use the EVE uirbvanny reactor to carry out the reaction of hydroformylation of another olefinic compound. Other than the hydroformylation used in the reaction, the reaction medium of which is to be treated. This also makes it possible to store the reaction medium to be treated or the reaction medium that has undergone treatment until reuse, if necessary.
    In addition, an increase in the activity of the complex rhodium catalyst as a result of the oxidizing agents of the invention according to the invention is not permanent with significant reversibility not only with the direct use of the treated catalyst, but also after storage for a sufficiently long period of time.
    Example 1 A hydroformylation reaction reaction medium is obtained by carrying out a continuous reaction of propylene hydroforming in the gas phase to produce butyraldehyde. The said process involves the supply of propylene, carbon monoxide and hydrogen to the reactor and conducting the reaction between them in the presence of reaction reaction.
    hydroformylation containing the resulting butyraldehyde, higher boiling aldehyde condensation products, which are byproducts serving as a solvent, free propyldiphenylphosphine, free triphenylphosphine, and a soluble rhodium-based hydroformylation complex catalyst consisting of a skip-bonded phosphate phosphate and a soluble rofi-based hydroformylation reaction catalyst, using a skip-bonded phosphate phosphate and a soluble rhodium-based hydroformylation catalyst for the oxidation of the aldehyde; Said reaction medium contains about 367 ppm. Rhodi (based on free metal), its catalytic activity is reduced to approximately 30% compared to fresh catalyst. The reaction is stopped as a result of stopping the supply of the initial gaseous reactants and removing almost all (more than 99.5%) of the indicated gaseous reagents from the reactor and highways working cycle. From the results of the analysis of the reaction mixture of the hydroformylation thus obtained, it can be seen that it contains about 14% by weight of butyraldehyde (reaction product), about 63% by weight of higher boiling aldehyde condensation products (by-product), about 0.9% by weight free propyldiphenylphosphine and about 17% by weight free triphenylphosphine, the remainder being said hzHb complex catalyst, triphenylphosphine oxide and more boiling organic reagents, for example aldehyde pentamers.
    The reaction reaction medium of hydroformylation is then subjected to oxidative treatment in the same reactor as a result of passing a gaseous mixture of nitrogen with air for about 14 hours at 70 ° C, a pressure of 4.08 atm, and at an average feed rate of 10.1 cubic feet (1 cu. ft of 0.0284 m3) of gas per gallon (1 gallon of 4.54 l) of the indicated reaction medium per hour, to obtain the reaction medium of the hydroforming reaction
    oxidative treatment, which contains about 8 May. % butyraldehyde (hydroformylation reaction product), about 0.05% by weight of free propyldiphenylphosphine and about 13% by weight of free triphenylphosphine in addition to the other specified components that were contained in the medium before oxygen treatment, wt.% of the initially contained amount of free propyldiphenylphosphine oxidized to produce the corresponding phosphine oxide, while only 23 wt.% of the initially contained free triphenylphosphine The reaction was to oxidize to the corresponding phosphine oxide at the indicated treatment with oxygen.
    From the results of the continuous reaction of hydroformylation of gaseous propylene with butyraldehyde, which used the oxidative processing of the reaction medium of the hydroformylation reaction, followed, it follows that its catalytic activity is about 85% 4 days after the start of the process and its value drops to about 50% by the second week of continuous operation (compared to the activity of a freshly prepared rhodium complex catalyst under the same conditions).
    Example 2. The reaction medium of the hydroformylation reaction is obtained by carrying out a continuous reaction of hydroformylation of propylene to produce butyraldehyde. This process involves the supply of propylene, carbon monoxide and hydrogen to the reactor and carrying out the reaction between them in the presence of the reaction medium of the hydroformylation reaction containing butyraldehyde (reaction product), the reaction by-products are higher boiling point aldehyde condensation products, acting as a solvent, free propyl diphenylphosphine, free triphenylphosphine, as well as soluble rhodium-based hydroformylation complex catalyst, consisting of rhodium, complexed with carbon monoxide but also triphenylphosphine. Said reaction medium contains about 183 ppm. give birth (based on the free metal), its catalytic activity is reduced to about 40% of the activity of the freshly prepared catalyst. The reaction is stopped as a result of the interruption of the supply of the initial gaseous reactants and the removal of practically all (more than 99.5%) of the indicated gaseous components from the reactor and lines of the operating cycle. From the results of the analysis of the reaction medium of the hydroformylation reaction, it follows that it contains about 22% by weight of butyraldehyde (reaction product), about 65% by weight of higher boiling by-products of aldehyde condensation, about 0.3% by weight of free propylene diphenylphosphine, and about 11% by weight The% free triphenylphosphine, the remainder being said rhodium complex catalyst, triphenylphosphine oxide and higher boiling organic components, for example aldehyde pentamers.
    This hydroformylation reaction reaction medium is then subjected to oxidative treatment in the same reactor as a result of passing a gaseous mixture of nitrogen and air (containing about 4% oxygen) through this medium for about 13 hours at 60-67 ° C and a pressure of 4.2 atm and at an average a feed rate of about 10.1 cubic feet of gas per gallon of said reaction medium per hour to form a reactionary hydroformylation reaction medium that underwent an oxidative treatment containing about 16% by weight of butrialdehyde (the product reaction), about 0.08 wt.% free propildifenilfosfina and about 8 wt.% of free triphenylphosphine, in addition to other components of the reaction mixture indicated that
    contained therein before said oxygen treatment. From the results of the analysis, it follows that about 74% by weight of the initially available amount of free propyldiphenylphosphine is oxidized to the corresponding phosphine oxide, while only about 20% by weight of the initially available amount of free triphenylphosphine is oxidized to the corresponding oxide as a result of this treatment with oxygen.
    Example 3. The reaction medium of the hydroformylation reaction is obtained by carrying out a continuous reaction of hydroformylation of propylene to produce butyraldehyde. This process involves supplying propylene, carbon monoxide and hydrogen to the reactor and conducting the reaction between them in the presence of the reaction medium of a hydroformylation reaction containing butyraldehyde (reaction product) and higher boiling condensation by-products of aldehydes acting as a solvent, free propyl diphenylphosphine, free triphenylphosphine, as well as a soluble complex catalyst for the reaction of hydroformylation based on rhodium, consisting of rhodium, complexed with carbon monoxide and triphenylphosphine nom. Said reaction medium contains about 234 ppm. give birth (based on free metal), its catalytic activity is reduced to about 40% of the activity of a freshly prepared catalyst. The reaction is stopped as a result of cessation of the supply of initial gaseous reactants and removal of almost all (more than 99.5%) of these gaseous components from the reactor and lines duty cycle. From the results of the analysis of the reaction medium of the hydroformylation reaction, it follows that it contains about 24% by weight of butyraldehyde, about 62% by weight of higher boiling point by-products of aldehyde condensation, about 0.3% by weight of free propyldiphenylphosphine and about 13% by weight of free triphenylphosphine, the residue consists of the said complex catalyst based on rhodium, triphenylphosphine oxide and higher boiling organic components, for example, aldehyde pentamers.
    The hydroformylation reaction reaction medium is then subjected to oxygen treatment in the same reactor as a result of passing a gaseous mixture of nitrogen and air containing
    about 4% of oxygen, through this mixture for 13 hours at 54 ° C - 65 ° C, at a pressure of 4.2 atm and an average feed rate of about 14.5 cu. Feet of said reaction medium per hour, to produce a reaction medium of hydroformylation reaction, subjected to an oxidative treatment, containing about 16% by weight of butyraldehyde (reaction product), about 0.1% by weight,% of free propyldiphenylphosphine and about 10% by weight of free triphenylphosphine, in addition to the rest of the components of the reactive mixture, which were contained in it before the specified treatment with oxygen. From the results of the analysis, it follows that approximately 65 wt.% Of the initially available amount of free propyldiphenylphosphine was subjected to
    0 to oxidation to the corresponding phosphine oxide, while only about 11% by weight of the initially available amount of free triphenylphosphine oxidized to the corresponding
    5 he oxide as a result of the specified treatment with oxygen.
    Example 4. A hydroformylation reaction reaction medium is prepared by carrying out a continuous reaction of hydro-forming a propylene gas to produce butyraldehyde. This process involves the supply of propylene, carbon monoxide and hydrogen to the reactor and carrying out the reaction between them in the presence of the reaction medium of the hydroformylation reaction containing butyraldehyde (the reaction product) and higher boiling by-products of condensation aldehydes, acting as a solvent, free
    0 propyldiphenylphosphine, free triphenylphosphine, as well as a soluble complex catalyst for hydroformylation reaction based on rhodium, consisting of rhodium, complexed with
    5 with carbon oxide and triphenylphosphine. Said reaction medium contains about 267 ppm. born on the basis of free metal, its catalytic activity is reduced to about 40% of
    0 activity of freshly prepared catalyst. The reaction is stopped as a result of cessation of the supply of the initial gaseous reactants and removal of practically all (more than 99.5%) of the indicated gaseous various components from the reactor and lines of the operating cycle. From the results of the analysis of the reaction medium of the hydroformylation reaction, it follows that it contains about 25% by weight of butyraldehyde (reaction product), about 60% by weight
    higher boiling by-products of aldehyde condensation, about 0.4% by weight of free propyldiphenylphosphine and about 14% by weight of free triphenylphosphine, the residue consists of said complex catalyst based on rhodium, oxide of triphenylphosphine and higher boiling organic components, for example aldehyde pentamers .
    The hydroformylation reaction reaction medium is then subjected to oxygen treatment in the same reactor as a result of passing a gaseous mixture of nitrogen and air (containing about 4% oxygen) through the medium for 13 hours at 54-60 ° C. a pressure of 4.2 atm and an average feed rate of about 14.7 cubic feet of gas per gallon of said reaction medium per hour, to produce a reaction medium of a hydroformylation reaction containing about 17 wt.% butyraldehyde (reaction product}, about 0.1 wt.% free propyldiphenylphosphine and about 11 May% free triphenylphosphine s in addition to the rest of the components of the reaction mixture that were contained in it before the indicated oxygen treatment. The free amount of free propyl diphenylphosphine was oxidized to the corresponding phosphine oxide, while only about 11% by weight of the initially available amount of free triphenylphosphine was oxidized to the corresponding oxide as a result of this oxygen treatment.
    Example 5. Conducting the subsequent reaction of hydroformylation of propylene gas to produce butyraldehyde, in which the combined
    the reaction medium obtained as a result of the oxidation according to examples 2-4 shows that it has a catalytic activity of about 68% after a 20-day continuous reaction (compared to the activity of a freshly prepared rhodium complex catalyst under the same conditions),
    Thus, the use of this method allows to increase the activity of the catalyst from 30 to 85% of the initial activity (see example 1).
    权利要求:
    Claims (1)
    [1]
    The invention method of producing oil aldehyde by hydroformylation of propylene with carbon monoxide and hydrogen in the presence of a catalyst, which is a mixture of born with c-triphenylphosphine, with the formation of the reaction mass containing oil aldehyde, high boiling by-products of condensation of oil aldehyde, propyl diphenylphosphine phosphine, nilphosphine and the rest, containing a complex rhodium catalyst, triphenylphosphine oxide and high-boiling organic components, followed by treatment with ion mass oxygen-containing gas at elevated temperature, characterized in that. to increase the activity of the catalyst, after the hydroformylation process is carried out, the hydroformylation reaction is stopped and the reaction mass is treated with an oxygen-containing gas under conditions different from hydroformylation at a temperature of 54-70 ° C and a partial pressure of oxygen of 10 - 10 atm, and the treatment is carried out that 63-94 wt.% propyl diphenylphosphine is converted to its corresponding oxide compound and 11-23 wt.% of triphenylphosphine is converted to triphenylphosphine oxide.
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    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/190,280|US4605780A|1980-09-24|1980-09-24|Reactivation of rhodium complex hydroformylation catalysts|
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