• 专利附录
  • 专利说明
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    • 专利摘要:
    The isolation and regeneration of catalysts of type I or II ClRh(CO)(PR3)2I HRh(CO)(PR3)3II, where the R's are identical or different hydrocarbon radicals, to give the catalysts in a pure form, is effected by regenerating aqueous rhodium salt solutions, as obtained on treating distillation residues of hydroformylation mixtures with oxygen-containing mineral acids and peroxides, by a method wherein the said aqueous rhodium salt solutions are treated with a cation exchanger, the latter is then separated from the solution, the absorbed rhodium ions are desorbed with hydrochloric acid, the hexachlororhodate solutions, containing hydrochloric acid, are reacted, in the presence of a water-soluble organic solvent and a tertiary phosphine PR3, with carbon monoxide, or with compounds which eliminate carbon monoxide, at from 0 DEG to 150 DEG C and from 1 to 5 bars, and the resulting complexes I or, if the process is carried out under hydrogenating conditions, the resulting complexes II, are separated off.
    公开号:SU898951A3
    申请号:SU772466670
    申请日:1977-04-04
    公开日:1982-01-15
    发明作者:Куммер Рудольф；Шнейдер Хейнц-Вальтер；Швиртен Курт
    申请人:Басф Аг (Инофирма)；
    IPC主号:
    专利说明:

    (5A) METHOD FOR REGEN CATALYST The invention relates to methods for regenerating rhodium-containing catalysts for the hydroformylation of olefins. A known method of regenerating rhodium-containing catalysts for hydroformylation of olefins by decomposing catalysts using water vapor at elevated temperatures p. However, the known method allows to obtain rhodium in an elementary form. Obtaining the active complex is difficult. Closest to the present invention is a method for regenerating rhodium-containing catalysts for hydroformylation of olefins by treating the residue containing the catalyst with acids, for example, nitric acid, and hydrogen peroxide. The aqueous phase containing the rhodium salt is isolated, the excess peroxide is destroyed by heating, and the aqueous solution is treated with carbon monoxide at O-ISO C and a pressure of 1-5 bar in the presence of organic-POLYTHILE RODIUM-CONTAINING roforming and one of the solvents and complexing agents — triphenylphosphine. An organic solution of the rhodium carbonyl complex is obtained, which can again be used in the hydroformylation reaction J. However, this method only allows rhodium to be extracted, catalyst regeneration is carried out under pressure in the system of two liquid phases and therefore does not proceed fast enough. In addition, this method allows one to obtain solutions in which the catalyst consists only of the central atom of the noble metal — rhodium and CO and L ligands are of zero valence, where L is a tertiary phosphine. Prefer complexes in which) L is replaced by halogen, as more stable. The aim of the invention is to increase the degree of extraction of rhodium. This goal is achieved by the described method of regeneration of the hydrogen-containing catalyst hydro389 for the formation of olefins, which is a complex of HRh (CO) (RK, o) t or ClRh (CO) (RQC) 2, where R is a phenyl group, by treating the residue containing the catalyst , nitric acid and hydrogen peroxide with further processing of the resulting aqueous solution with carbon monoxide at 0-150 C and pressure of 1-5 bar in the presence of an organic solvent and triphenylphosphine, the resulting aqueous solution is passed through sulfo cation exchanger by the next desorption of the adsorbed ions with hydrochloric acid, the essence of the method is as follows. The distillation residues obtained by hydroformylation in the presence of rhodium catalysts consist mainly of volatile aldehydes, alcohols, aldols, carboxylic acids and esters and usually contain; 0,001-1 noble metal. 100 weight.h. such a residue, it is advisable to subject the reaction at 20120 C with thorough stirring C 10-100 weight. Part 1 - aqueous nitric acid and 10-100 parts by weight. hydrogen peroxide. In the oxidative treatment of hydroformylation residues, rhodium virtually quantitatively passes as the aqueous phase. Suitable cation exchangers are crosslinked polymers having sulfonic acid groups or carboxyl groups, for example, divinylbenzene styrene resins. These and similar cation exchangers are known by the names Amberlite and Levatite. The amount of cation exchanger is preferably set in such a size that 10,100 mole equivalent of acid is per mol of K 1. Since the method receives approximately 0.01 to 0.5 weight. aqueous solutions of Rh. In practice, this means that about 10-1000 g of cation exchanger are used per liter of this solution. The treatment with cation exchanger is preferably carried out at room temperature as follows: the aqueous solution is mixed with cation exchanger for 30-120 minutes, or the solution is passed through an ion exchange column while observing the corresponding residence time. The remaining solution containing, if appropriate, eilfe peroxides, free of rhodium, can be used to treat additional hydroformylation residues. According to the proposed method, predominantly hydroformylation residues are treated in portions with a limited volume of the aqueous phase, and the regenerated solutions again replenish with the same amount of peroxide and acid that corresponds to consumption by oxidation. For desorption, the cation exchanger is reacted, preferably with a 20-100 molar amount, based on rhodium, 1-5 N, hydrochloric acid. In the subsequent step and the process, the rhodium in the form of RhC anions is converted by phosphines PR-j and carbon monoxide in the presence of water-soluble solvents in the hydrochloric acid phase into complexes ClRh (Co) (PR) 2 (I) or, if additionally under hydrogenating conditions, into HRh (Co) (PR) (I) complexes. From chitium to rhodium, the amount of phosphine corresponds to at least stoichiometric formulas, 1 or 11, however, it is advantageous to add phosphine in 1-100-fold molar excess. The function of the anhydrous organic solvent is to maintain the free phosphine in the aqueous-organic phase in a dissolved state. Thus, the amount of solvent depends on the amount of aqueous hydrochloric acid solution, on the type of solvent, on the type and amount of phosphine and, to some extent, on the type and amount of other pre-treatment dependent constituents in the aqueous phase. This number varies from case to case, but it can easily be installed by several preliminary tests on standard solutions that do not contain precious metals. It is advisable not to exceed the required minimum amount, however, according to existing data, the result of the method does not deteriorate even if the water content in the system is only 10 weight. For example, acetone, tetrahydrofuran and dioxane are suitable as water-soluble organic solvents, and first of all, alcohols with 1-A carbon atoms, for example, methanol, ethanol, propanol, isopropanol, n-butan-1-ol, n-butan-2-ol, iso-buta -1-ol and iso-butane-2 -ol. It is recommended to dissolve the phosphine in a solvent and in this form add hexachloro-date to the aqueous solution. The choice of phosphine PR depends on the type of hydroformylation reaction in which rhodium catalysis should be used. It is also preferable to use type I or L catalysts in which organic phosphine residues mean the same or different alkyl, aralkyl, ari / or alkylaryl residues containing up to 12 carbon atoms, with the total number of carbon atoms in phosphine found to be between 12 and 36 "All these phosphines, whose carbohydrate-like residues may also have halogen atoms as substitutes or which may be interrupted by oxygen atoms, have in the proposed method of catalyst regeneration the essential property that they are in a homogeneous aqueous-organic medium, they are sufficiently soluble; however, in this medium, together with rhodium and carbon monoxide, they form very insoluble halogen- or hydride complexes. I If phosphines are very difficult to dissolve in an aqueous-organic medium, then the combined use of dispersants is possible. In this case, highly dispersed dispersions are obtained which, however, behave as solvents. In some cases, it is recommended to heat the aqueous-organic solution prior to carbonylation so that the phosphine has the opportunity to attach to the rods. Then, through the aqueous-organic solution containing the rhoxi xpor-phosphine complex is passed at 0-120 ° C and 1-5 bar, preferably at a temperature of boiling solution at normal pressure, carbon monoxide. In this case, the complexes of I fall out almost quantitatively, in an appropriate case, together with one part of the excess phosphine. Instead of carbon monoxide, CO splitting compounds can also be used, for example formaldehyde. If the carbonylation is carried out under hydrogenation conditions, the same insoluble JT hydride complexes are obtained. For this, either hydride ions reducing agents, such as sodium borohydride, are used at 0100 ° C and normal pressure, or hydrogen at O-IStTC and a pressure of 1-300 bar. Chlorine complexes I can also be additionally converted to hydride complexes and. dissolving them in water-soluble organic solvents, hydrogenating and separating by adding water. The regenerated catalysts 1 or I are returned to the hydroformylation process. EXAMPLE To 1000 g of the distillation residue formed during 8 months with continuous hydroformylation of propylene, preferably in the form of n-butyraldehyde and containing mg of rhodium, preferably in the form of HRh (Co) (PR) s complex (R-phenyl), is mixed with UOO g 1 hydrochloric acid and 300 g of hydrogen peroxide, first 20 hours at room temperature, and then another h at C0-60 C. At the same time, about 98% of the bile is transferred into the aqueous acid phase, which is then passed through a column for 60 minutes with 250 g of sulfo group-containing cation exchanger (Amberlite® IR120, 1.9 mol. eVo acid per liter) o The remaining rhodium-free solution is slightly concentrated with nitric acid and hydrogen peroxide to the initial amount and initial concentration, and is used to process an additional 1000 g of distillation residue. After 10 cycles of this kind, i .e. after processing, 10 kg of residue is condensed, thus, in the cation exchanger approximately 3, + g of rhodium. Then the rhodium is washed out with 1000 ml of 3N hydrochloric acid, then the solution is concentrated to 300 ml and 600 ml of iso-propanol and 26.5 g of triphenylphosphine are added and treated with carbon monoxide under normal pressure for 15 minutes. After cooling, yellow crystals of CIRh are isolated ( Co) (PRg) 2 The recovery of regenerated rhodium constitutes, at all stages of the process, 97. The reduction of the chlorine complex in isopropanol / water with sodium boronate with additional triphenylphosphine gives a quantitatively corresponding hydride complex.
    invention formula
    The method of regeneration of the rhodium-containing catalyst for hydroformylation of olefins, which is the 5th complex of HRh (Co) (P) or ClRh (Co) (PRj), where R is a phenyl group, by treating the residue containing the catalyst with nitric acid and hydrogen peroxide to further form By treating the resulting aqueous solution with carbon monoxide at 0-150 0 and a pressure of 1-5 bar in the presence of an organic solvent and triphenylphosphate898951
    Finish, characterized in that, in order to increase the degree of extraction of rhodium, the resulting aqueous solution is preliminarily passed through sulfonic cation resin, followed by desorption of the adsorbed ions with hydrochloric acid.
    Sources of information taken into account in the examination 1.Patent of Germany No. 2262885, class.42 1 3/09, published in 1976
    2. US patent number, class., Published. 1970 (prototype).
    V,
    权利要求:
    Claims (1)
    [1]
    Claim
    The method of regeneration of a rhodium-containing catalyst for hydroformylation of olefins, which is a complex of HRh (Co) (RId) 3 or ClRh (Co) (PRj) 2> where R is a phenyl group by treating the residue containing the catalyst with nitric acid and hydrogen peroxide with further conversion by working of the resulting aqueous solution with carbon monoxide at 0-150 ° С and a pressure of 1-5 bar in the presence of an organic solvent and triphenylphos
    898951 8 fin, characterized in that, in order to increase the degree of extraction of rhodium, the resulting aqueous solution is preliminarily passed through sulfocationite with subsequent desorption of adsorbed ions with hydrochloric acid <,
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    同族专利:
    公开号 | 公开日
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    NL180482C|1987-03-02|
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    JPS52123397A|1977-10-17|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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