KR840000389B1 - Hydroformylation catalyst reactivation - Google Patents

Abstract

Hydroformylation of olefins with H2 and CO to produce aldehydes uses water-soluble rhodium complex catalyst in the presence of a reaction redium, which is composed of at least 10 moles of triarylphosphine to 1 mole of rhodium. Partially deactivated rhodium catalyst and the reaction medium are distillated at 20-350≰C and 1,000-l×10-6 mmHg, from which concentrated rhodium complex is used as the catalytic rhodium.

Description

Method for preparing aldehyde by hydroformylation

The present invention relates to a rhodium complex using a rhodium complex concentrate containing a reactivated rhodium derived from a waste hydroformylation reaction medium containing a partially deactivated rhodium complex catalyst and triarylphosphine as a source of rhodium for the catalyst. An improved process for preparing aldehydes by hydroformylating olefins in the presence of a catalyst is provided.

Reactions of aldehydes by hydroformylation (oxo synthesis) of olefins with carbon monoxide and hydrogen in the presence of rhodium complex catalysts and free triarylphosphine are well known in the art.

For example, U.S. Patent No. 3,527,809 discloses aldehydes in high yield by hydroformylating olefins at low and low pressure conditions in the presence of a rhodium complex catalyst and free triaryl phosphine to yield aldehydes in the product. A hydroformylation process with a high ratio of normal isomers to aldehyde isomers is described.

Also, under hydroformylation conditions, some of the aldehydes produced may be condensed to produce by-products, ie, high boiling point aldehyde condensation products such as aldehyde dimers or trimers. U.S. Patent No. 4,148,830, which is hereby incorporated by reference in its entirety, proposes the use of such high boiling liquid aldehyde condensation products as reaction solvents for catalysts. Some of the aldehyde products cause various reactions, as shown below for n-butyraldehyde for explanation, in particular as described in this U.S. Patent No. 4,148,830:

In addition, aldol (I) may cause the following reactions.

In the above reaction scheme, the names in parentheses of aldol (I), substituted acrolein (II), trimer (III), trimer (IV), dimer (V), tetramer (VI) and tetramer (iii) are merely for convenience. I used it. Aldol (I) is produced by aldol condensation reaction; Trimers (III) and tetramers are produced through the Tischenko reaction; The trimer (IV) is produced by a transesterification reaction, and the dimer (V) and tetramer (VI) are produced by a disproportionation reaction. The main condensation products are trimers (III), trimers (IV) and tetramers (Ⅶ), and other products are present in small amounts. Such condensation products thus contain significant amounts of hydroxyl compounds, as demonstrated as trimers (III) and (IV) and tetramers.

Similar condensation products are prepared by isobutyraldehyde self-condensation and other compounds are further prepared by condensing one molecule of n-butyraldehyde with one molecule of isobutyraldehyde. Condensation of a normal / isobutyraldehyde mixture as one molecule of n-butyaldehyde generates an aldolization reaction with one molecule of isobutyraldehyde according to two different methods to produce two different kinds of aldols and (iii). The total number of aldols that can be produced from the reaction is four.

Aldol (I) continues condensation with isobutyraldehyde to form a trimer which is an isomer relationship with trimer (III), and the corresponding condensation produced by the self-condensation of two molecules of aldol and (i) and isobutyraldehyde Aldols can continue to react with normal or isobutyr aldehydes to produce the corresponding isomeric trimers. This trimer may continue in a reaction similar to trimer (III) to produce a complex mixture of condensation products.

In addition, U.S. Patent Application No. 776,934 (Belgium Patent 853,377), filed on March 11, 1977, which is hereby incorporated by reference in its entirety, describes a liquid hydroformylation reaction using a rhodium complex catalyst. The aldehyde reaction products and some of their high boiling point condensation products are separated and recovered in vapor form from the liquid (or solution) zone containing the catalyst under the reaction temperature and pressure. Aldehyde reaction products and condensation products are condensed from the off-gas of the reactor in the product recovery zone and unreacted starting materials in the vapor phase (e.g. carbon monoxide, hydrogen and / or alpha-olefins are recycled from the product recovery zone to the reaction zone). By combining the recycle gas from the stand with the starting material replenishment feed and recycling a sufficient amount to the reaction, C ₂ to C ₅ olefins can be used as the alpha olefin starting material to balance the liquid material in the reactor and thereby at least the aldehyde product. Almost all high-boiling condensation products obtained from the self-condensation of can be separated from the reaction zone at least at the same rate as their production rate.

In particular, the patent application 776,934 describes a process for the preparation of aldehydes containing 3 to 6 carbon atoms, in which an alpha olefin containing 2 to 5 carbon atoms is introduced in the liquid phase together with hydrogen and carbon monoxide at the aforementioned temperature and pressure. Reaction was carried out through a reaction zone containing a rhodium complex catalyst dissolved therein, followed by separation of the gas phase from the reaction zone, which was sent to a product separator, where the liquid aldehyde containing the product was condensed. It has been described for use from the reaction starting materials and by recycling the unreacted starting materials obtained from the product separator to the reaction zone.

It is well known that under hydroformylation conditions, rhodium hydroformylation catalysts undergo deactivation even in the absence of intrinsic catalyst poisons. United States Patent Application No. 762,336 (Belgian Patent No. 863,268), filed on January 25, 1977, filed on January 25, 1977, which is incorporated herein by reference in its entirety, deactivates the rhodium hydroformylation catalyst under hydroformylation conditions in which almost no artificial catalyst poison is present Is an intrinsic deactivation due to a combination of temperature, molar ratio of phosphine ligands to rhodium and partial pressures of hydrogen and carbon monoxide. Such intrinsic deactivation is due to low temperature, low carbon monoxide partial pressure and catalytically active rhodium. It has been described that by setting and managing the high molar ratio of hydroformylation conditions of the free triarylphosphine ligands, the reduction or near prevention can be achieved.

The method of limiting deactivation of the catalyst by adjusting the carbon monoxide partial pressure, temperature and molar ratio of free triarylphosphine to catalytically active rhodium is described as follows.

As an example of a triarylphosphine ligand, the characteristic relationship between these three parameters and catalyst stability in triphenylphosphine is defined by the following equation.

In the above formula

F = stability factor

e = Naperian log base (2.718281828)

y = K ₁ + K ₂ T + K ₃ P + K ₄ (L / Rh)

T = reaction temperature (℃)

P = partial pressure of carbon monoxide (psia)

L / Rh = free triaryl phosphine; Catalytically active rhodium molar ratio

K ₁ = -8.1126

K ₂ = 007 919

K ₃ = 0.02718

K ₄ = -0.01155

As described in Patent Application No. 762,336, an olefin reaction factor should be applied to obtain a stable factor under actual hydroformylation conditions. Olefins generally aid in catalyst stabilization and the effect of olefins on catalyst stability has been fully described in the patent application. In other triaryl phosphines, the above relation is almost the same except that the constants K ₁ , K ₂ , K ₃ and K ₄ change. Those skilled in the art can determine the characteristic constants for other triarylphosphines with minimal experimentation as fully described in the patent application.

The presence of alkyldiarylphosphines (e.g., propyldiphenylphosphine or ethyldiphenylphosphine) in the rhodium catalyst hydroformylation of alpha-olefin propylene inhibits the catalytic productivity, i.e., the rate of production of aldehydes, which are required products. It has also been found that. In particular, when a small amount of propyldiphenylphosphine or ethyldiphenylphosphine is added to the rhodium hydroformylation solution, the production rate of butyraldehyde from propylene is remarkable compared with the reaction rate in the presence of alkyldiaryl phosphines. Is reduced.

In the presence of alkyldiaryl phosphines in rhodium-catalyzed hydroformylation, catalyst productivity is reduced, but the stability of such rhodium complex catalysts can be promoted by providing alkyldiarylphosphines in the reaction medium. United States Patent Application No. 762,335 (Belgian Patent No. 863,267), filed on January 25, points out that the reaction conditions must be strengthened to compensate for the reduced productivity of the catalyst while maintaining improved catalyst stability. have.

Patent Application No. 762,335 discloses that when triarylphosphine ligands are used for hydroformylation of alphaolefins, a small amount of alkyldiarylphosphine is produced in the reaction system and its 'alkyl' groups are used in the hydroformylation process. It is pointed out that the 'aryl' group derived from the alpha-olefin is the same as the aryl of the triarylphosphine.

The patent application No. 762,335 describes a rhodium complex catalyst produced when the alkyldiarylphosphine ligand is present in a liquid reaction medium containing a rhodium complex catalyst consisting mainly of rhodium complexed with carbon monoxide and triarylphosphine ligands. Consists mainly of rhodium complexed with one or both of carbon monoxide and triarylphosphine ligands and alkyldiarylphosphine ligands, where the term "consists mainly of" carbon monoxide, triarylphosphine and alkyldiaryl phosphates In addition to fins or carbon monoxide and triarylphosphines or alkyldiarylphosphines, they describe clues intended to be included, not intended to exclude hydrogen complexed with rhodium. However, this term means that other substances in the amounts that damage and deactivate the catalyst are excluded. Patent application 762,335 describes that particularly advantageous results can be obtained when the total amount of free phosphine ligands in the liquid reaction medium is at least about 100 moles per mole of catalytically active rhodium metal present in the rhodium complex catalyst.

Thus, in the case of the patent application, despite the apparent advantages, the rhodium complex catalyst loses its activity during use (ie, partially deactivated), and after prolonged use, the catalytic activity is no longer sufficient to economically advance the hydroformylation reaction. It is degraded to an undesired degree, so the catalyst has to be discarded and replaced with a new catalyst. Therefore, in view of the high unit cost of rhodium, reactivation of such partial deactivation catalysts and rhodium recovery from such catalysts are extremely important in this field.

According to the present invention, a rhodium complex concentrate derived from a spent hydroformylation reaction medium containing a partially deactivated rhodium complex catalyst contains a reactivation rhodium and the copper concentrate is a catalyst precursor in a hydroformylation reaction. It was found that it can be used as a material to significantly increase the reaction rate than when using the partial deactivation catalyst. Unlike the prior art, the present invention can reactivate Rhodium of a partial deactivation catalyst without using a chemical compound such as acid, and it is technically very effective that Rhodium metal is not recovered before use. . It is an object of the present invention to improve the preparation of aldehydes by hydroformylating olefins in the presence of a rhodium complex catalyst and triarimphosphine, wherein the feature is the preparation of waste hydroformylation reaction medium as rhodium source of catalyst. One rhodium complex concentrate is used.

In addition, the present invention provides a method for preparing a rhodium complex from a rhodium complex concentrate prepared from a waste hydroformylation reaction medium as well as preparing a hydroformylation medium composed of a reactivated rhodium complex and triarylphosphine. Are included. Other objects and advantages of the present invention will become apparent from the following description and the claims.

Another object of the present invention includes a process for preparing a hydroformylation medium containing rhodium complex and triarylphosphine, wherein the rhodium complex concentrate is at least about 10 moles of glass tree per mole of rhodium present in the medium. Prepared by mixing with a sufficient amount of triarylphosphine to be present arylphosphine, the rhodium complex concentrate is a waste hydroformylation reaction medium containing a partially deactivated rhodium complex catalyst and free triarylphosphine from about 20 to Prepared by separation and concentration into at least two streams using distillation at a temperature of about 350 ° C. and a pressure of about 1000 to about 1 × 10 ⁻⁶ mmhHg.

One stream here is a rhodium complex concentrate (e.g. distillation residue) containing most of the rhodium of the catalyst and concentrated to about 0.1 to about 30% by weight of the spent hydroformylation reaction medium and the other stream is mainly It consists of one or more volatile distillates of the spent hydroformylation reaction medium.

The above method for preparing a hard hydroformylation medium also preferably uses a sufficient amount of solvent such that the amount of rhodium contained in the liquid hydroformylation medium is in the range of about 25 to about 1000 ppm in terms of metal atoms.

Another of the general concepts of the present invention may be described as a hydroformylation medium consisting of at least 10 moles of freetriarylphosphine and rhodium complexes per mole of rhodium contained in the hydroformylation medium, which medium may also be described. It is preferable that the amount of rhodium contained in the medium include a solvent for the complex such that the amount of rhodium in terms of metal atoms is in the range of about 25 to about 1000 ppm, wherein the rhodium complex is a partially deactivated rhodium complex catalyst and a free triaryl. The waste liquid hydroformylation reaction medium containing phosphine is at least two streams distilled at a temperature of about 20 to about 350 ° C. and a pressure of about 1000 to about 1 × 10 ⁻⁶ mmHg, where one stream is waste hydroformylation. Rhodium complex concentrate (e.g. distillation residue) containing most of the rhodium in the catalyst, concentrated to about 0.1 to about 30% by weight of the reaction medium The remaining stream is derived from a rhodium complex concentrate prepared according to the process, which is characterized in that it is concentrated separately to one or more volatile distillates of the spent hydroformylation reaction medium.

An object of the present invention is to prepare aldehydes by hydroformylating olefins as hydrogen and carbon monoxide in the presence of a hydroformylation reaction medium consisting of at least 10 moles of free triarylphosphine and soluble rhodium complex catalyst per mole of catalytically active rhodium. An improved manufacturing method is provided.

The nature of the inventive process is that as a source of rhodium for this catalyst, a waste liquid hydroformylation reaction medium containing a partially deactivated rhodium complex catalyst and triarylphosphine is used at a temperature of about 20 to about 350 ° C. and about 1000 to about 1 Rhodi containing most of the rhodium in the catalyst, concentrated by at least two separate streams by distillation at a pressure of 10 ⁻⁶ mmHg, where one stream is concentrated from about 0.1 to about 30% by weight of the spent hydroformylation reaction medium. Um complex concentrates (e.g. distillation residues), the remaining stream consisting mainly of one or more volatile distillates of the waste liquid hydroformylation reaction medium) The use of concentrates.

As described above, the novelty of the present invention is found to be reactivated or reproducible by concentrating the waste hydroformylation reaction medium containing the partially deactivated rhodium complex catalyst and the free triarylphosphine into the rhodium complex concentrate by distillation. To the end. The term " waste hydroformylation reaction medium " herein refers to at least partially deactivation of the catalyst in the process of hydroformating olefins with carbon monoxide and hydrogen in the presence of a rhodium complex catalyst and free triarylphosphine. Hydroformylation reaction medium or part thereof containing the rhodium complex catalyst and freetriaryl phosphine of any process operated to an extent. In general, it is preferable to concentrate the hydroformylation reaction medium in which the rhodium complex catalyst is deactivated so that the hydroformylation process can no longer be economically performed. However, the enrichment process in the present invention must be carried out in such a way as it can proceed in any waste hydroformylation medium, if necessary, i.e. containing at least partially deactivated rhodium complex catalyst, for example, a catalyst that is somewhat less active than the original catalyst. You do not have to wait until it is completely destroyed. The degree of deactivation of the catalyst can be measured at any point in the hydroformylation reaction by comparing the conversion to the product based on the catalyst with the conversion obtained using the new catalyst.

As described in the above prior art method, it is well known to produce an aldehyde by subjecting an olefin to a hydroformylation reaction with a rhodium complex catalyst in the presence of free triaryl phosphine. Therefore, the reaction conditions and components of the hydroformylation process as well as the specific hydroformylation process for preparing aldehydes from olefins derived from the waste hydroformylation reaction medium used in the present invention are not important features of the present invention. This is because it is only a means for providing a waste hydroformylation reaction medium used as a starting material of the invention. In general, however, it is preferred to concentrate the waste hydroformylation reaction medium derived from the processes described in the above-mentioned U.S. Patent Nos. 3,527,809 and U.S. Patents 762,335 and 776,934.

Therefore, the waste hydroformylation reaction medium usable in the present invention is composed of a partially deactivated rhodium complex catalyst and a free triaryl phosphine, and the material added from the outside in the hydroformylation process or spontaneously generated during the reaction process is added. It may contain. Such additional inclusions include, for example, phosphate produced in the reaction system by alkyl-substituted phosphines and external oxygen, as well as catalyst solvents such as olefin starting materials and aldehyde products of this process, high boiling point liquid condensation products of the aldehydes. Fin oxides are included.

As seen in the above-mentioned prior art, such hydroformylation reaction is preferably carried out in the presence of a rhodium complex catalyst and free triarylphosphine mainly composed of rhodium complexed with carbon monoxide and triallylphosphine ligand. If the hydroformylation reaction is continued, an alkyl-substituted phosphine of the general formula (I) wherein R is alkyl radical, R 'is alkyl or aryl radical and R' 'is aryl radical is produced in the reaction system,

At this time, the amount of production is continuously increased during the hydroformylation reaction, and the alkyl-substituted phosphine ligand having a larger affinity than triarylphosphine for rhodium also binds to the rhodium in itself. Rhodium complexed mainly with carbon monoxide, triarylphosphine ligands and / or alkylsubstituted phosphine ligands (i.e., one or both of triarylphosphine ligands and alkylsubstituted phosphine ligands) in the liquid reaction medium in the densification process. To form a rhodium complex catalyst consisting of.

Such alkyl-substituted phosphines in the spent hydroformylation reaction medium used in the present invention may be present as a result of the optional addition during the initial hydroformylation reaction, if necessary, as described in US Pat. No. 762,335, above.

Therefore, the partially deactivated rhodium complex catalyst present in the waste hydroformylation medium used in the present invention may be any catalyst obtained in the hydroformylation reaction in which the rhodium complex catalyst is used. Preferred spent hydroformylation reaction media are those containing partially deactivated rhodium complex catalysts consisting mainly of rhodium complexed with carbon monoxide and triarylphosphine ligands. In particular, the term "composite" refers to a coordination compound formed by combining one or more electron-like moieties or atoms that may be present independently with one or more electron-poor molecules or atoms that may be independently present. Triorganophosphorus ligands, whose personnel have one usable lone pair, can form coordination bonds with rhodium. In particular, the term “consist of mainly” is not intended to exclude, but rather to exclude, hydrogen, which is complexed with rhodium in addition to alkyl-substituted phosphines as well as carbon monoxide and triarylphosphine when present in the reaction medium, The hydrogen and carbon monoxide are derived from minority and carbon monoxide gases that are part of the hydroformylation process. It is also not intended to limit the invention to the way in which rhodium complexes with these phosphines, since it is sufficient for the purposes of the present invention to simply point out that the preferred partially deactivated rhodium catalyst is a complex. U. S. Patent No. 3,527, 809 and Patent Application No. 762, 335 described above describe the principle of forming such ligand complexes with rhodium.

The second principal component present in the waste hydroformylation reaction medium used in the present invention is free triarylphosphine. As described above, the hydroformylation reaction preferably proceeds in the presence of free triarylphosphine, that is, triarylphosphine which is not complexed with rhodium atom in the complex catalyst. Generally such hydroformylation reactions can be carried out in the presence of at least 10 moles of free triarylphosphine ligands per mole of catalytically active rhodium present in the rhodium complex catalyst, but are preferably present in significantly larger amounts, such as at least 50 moles. And more preferably in the presence of at least 100 moles of free triarylphosphine per mole of catalytically active rhodium. As is well known, the upper limit of the amount of free triarylphosphine ligand used is not particularly limited, and mainly depends on commercial and economical viewpoints.

Whether it forms a complex with rhodium or is in the free state, the triarylphosphine present in the hydrohydroformylation reaction medium used in the present invention, as well as the triarylphosphines and reactions listed in the above-mentioned prior art Any triarylphosphine may be used as long as it is suitable for the hydroformylation reaction. Triarylphosphine ligands that can be used include triphenylphosphine, trinaphthylphosphine, tritolylphosphine, P- (N, N-dimethylamino) phenyl diphenylphosphine, tris (P-biphenyl) -force Pins, tris (P-methoxyphenyl) phosphine and the like. Dual triphenylphosphine is the most preferred triarylphosphine ligand.

In particular, alkyl-substituted phosphines such as formula (I) may also be present in the hydroformylation reaction medium usable in the present invention. Such alkylsubstituted phosphines, which may be previously added to the hydroformylation reaction if necessary, are usually derived from the particular olefins that are hydroformylated and the specific triarylphosphines used in the hydroformylation reaction. Indeed, hydroformylation of propylene according to the preferred recipe described in US patent application 776,934 results in the production of propyldiphenylphosphine as well as some measurable butyldiphenylphosphine.

Thus, the alkylredcal of this alkyl-substituted phosphine can be any alkyl radical having from 2 to 20 carbon atoms and more preferably from 2 to 10 carbon atoms. These may be straight or branched chains and may contain substituents or groups which are hardly impeded by the inventive process, such as hydroxy and alkoxy radicals. Examples of such alkyl radicals include ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, octadecyl, 2-ethyl-hexyl, eicosyl, 3-phenyl-propyl, 3-hydroxy Hydroxypropyl, 4-hydroxyhexyl, 4-hydroxyoctyl, 2-ethoxyethyl, 2-methoxyethyl, 3-ethoxypropyl and the like.

Particularly the most preferred alkyl radicals of alkylsubstituted phosphines are ethyl, propyl, butyl and pentyl, with preference being given to hydroformylation of alphaolefins containing generally 2 to 5 carbon atoms. Similarly, the aryl radicals of alkylsubstituted phosphines correspond to the aryl groups of the triarylphosphine ligands used in the hydroformylation reaction as described above, with the preferred aryl radicals being phenyl radicals derived from triphenylphosphine. Thus the most preferred alkylsubstituted phosphines are ethyldiphenylphosphine, propyldiphenylphosphine and butyldiphenylphosphine, with propyldiphenylphosphine being particularly preferred. However, the precise description or discussion of the process by which these alkyl-substituted phosphines are produced in the reaction solution itself is beyond the intention of the applicant, and for the purposes of the present invention only their production in the liquid liquid hydroformylation reaction medium which can be used in the present invention and The fact that it is possible is enough.

Rhodium complex catalyst, triarylphosphine, which may be present in the phenhydroformylation reaction medium usable in the present invention. And the amount of alkylsubstituted phosphine is not specifically determined since this amount only depends on the hydrohydroformylation reaction medium to be concentrated. Therefore, the hydrohydroformylation reaction medium usable in the present invention is a hydroformylation reaction medium of an olefin, especially an alphaolefin, containing 2 to 20 carbon atoms composed of a partially deactivated rhodium complex catalyst and a free triaryl phosphine. Any may be good. Similarly, the amount of partially deactivated rhodium complex catalyst, triarylphosphine and alkylsubstituted phosphine present in the phen hydroformylation medium, from which the hydroformylation process for preparing rhodium complex concentrates usable in the present invention. The amount of the corresponding component produced during the reaction itself, which was used from the beginning in the reaction medium of In general, the amount of alkylsubstituted phosphine present in the phenhydroformylation reaction medium usable in the present invention ranges from 0 to about 20 weight percent, more preferably from about 1 to 10 percent of the total weight of the effluent medium, The content of triarylphosphine ligands can vary from about 0.5% to about 40% by weight or more of the total weight of the media. As described more fully in US Patent Application No. 40,913, filed May 21, 1977 and US Patent No. 108,279, filed December 28, 1979, which is incorporated herein by reference in its entirety, the concentration process used in the present invention. Prior to the introduction of the fermentation medium, such phosphine compounds in the ferhydroformylation reaction medium can be removed using aqueous maleic acid or maleic anhydride solution if necessary. However, such pre- removal of phosphine is not necessary to obtain the results required by the present invention described herein. The amount of partially deactivated rhodium complex catalyst present in the phenhydroformylation reaction medium usable in the present invention as well as the minimum amount (catalyst amount) required to continue to catalyze the hydroformylation reaction from which the effluent medium usable in the present invention is derived is You have to go over it. In general, the rhodium concentration in the media is in the range of about 25 ppm to about 1000 ppm and more preferably about 50 ppm to about 400 ppm in terms of rhodium free metal.

Since such hydroformylation reaction is usually carried out in the presence of a solvent for the rhodium complex catalyst, the hydrohydroformylation medium usable in the present invention also contains the same amount of the solvent for the catalyst so that this solvent is subjected to this hydroformylation reaction. It may be used in a liquid reaction medium of and is preferably used. Such solvents are well known in the art and include the solvents described in U. S. Patent No. 3,527, 809, and more preferably, their preparation methods are described in more detail in U. S. Patent Nos. 776, 934 and 4,148, 830 above. High boiling liquid aldehyde condensation products. Therefore, the amount of solvent present in the phenhydroformyl reaction medium usable in the present invention is not critical to the present invention and is preferably an amount used in the liquid reaction medium of the hydroformylation reaction or maintained in the reaction system. Thus, generally, the amount of solvent present in the media is in the range of about 10 to about 95 parts by weight relative to the total weight of the media.

The phenhydroformylation reaction medium usable in the present invention also contains at least some of the aldehyde products produced by the particular hydroformylation reaction from which the waste medium is derived. For example, the aldehyde product produced by hydroformylation of propylene is butyraldehyde. The amount of such aldehyde product present in the waste medium depends, of course, only on the particular hydroformylation reaction. Such waste media generally contain from about 0.1 to about 30% by weight of the aldehyde product, based on the total weight of the waste medium. Of course, the spent hydroformylation reaction medium also contains a small amount of unreacted olefin starting material and phosphine oxides corresponding to the phosphines present in the hydroformylation process, which is usually produced by external oxygen during the reaction. It is formed within itself.

As described above, the rhodium complex concentrates usable in the present invention are subjected to distillation of the waste hydroformylation reaction medium at a temperature of about 20 to about 350 ° C. and about 1000 to about 1 × 10 ⁻⁶ mmHg as defined above. Prepared according to a process characterized in that it is separated and concentrated to at least two streams, wherein one stream is concentrated to about 0.1 to about 30% by weight of the spent hydroformylation reaction medium and contains most of the rhodium in the catalyst. Um complex concentrates (eg distillation residues) and the remainder of the stream consist mainly of one or more volatile distillates of the spent hard hydroformylation reaction medium. More preferably, the waste hydroformylation reaction medium is distilled to produce a rhodium complex concentrate of about 1 to about 10 weight percent, and most preferably about 2 to about 6 weight percent of the waste media weight.

The distillation process is preferably carried out in two stages, and the first stage is a waste hydroformylation reaction at a temperature of about 20 to 250 ° C., preferably 20 to 190 ° C., and about 1000 to about 0.1 mmHg, and preferably 150 to 0.5 mmHg. The medium concentration is concentrated to about 3 times, and the second step of distillation is about 25 to 350 ° C., preferably about 150 to 300 ° C. temperature and about 100 to 1 × 10 ⁻⁶ mm Hg preferably about 20 to 0.1 mm Hg The bottom or residual oil product of the first stage is further concentrated under pressure, resulting in about 1000 to about 50,000 ppm more preferably about 1,500 to about 15,000 ppm and most preferably about 2,000 to 12,000 ppm in terms of free metal rhodium. Prepare the desired rhodium complex concentrate.

In the first distillation step, most of the volatiles, such as aldehyde products, present in the waste hardened formylation medium are distilled off, and these low boiling volatiles are effective for most of the nonvolatile (high boiling) materials in the second distillation step. This is because it interferes with maintaining the low pressure needed for removal. Of course, most of the volatiles thus separated (eg aldehyde products) may be recovered from the distillate stream by conventional techniques and, in some cases, discarded.

In the second distillation step, the depressurization condition described above is performed by taking the partially deactivated rhodium complex catalyst in the waste hydroformylation reaction medium and the liquid residue obtained in the first distillation step containing a high boiling point material such as a solvent and a phosphine ligand. Distillation is continued under the present invention to distill off the remaining high boiling volatiles. The necessary rhodium complex concentrate usable in the present invention is thus recovered as the distillation residue of the second stage distillation and contains most of the rhodium in this partially deactivated catalyst (50 weight of rhodium weight in the catalyst). At least%, preferably at least 90% by weight). In consideration of economics, it is most preferable that almost all of the rhodium (97 wt% or more) in the partially deactivated catalyst is contained in the rhodium complex concentrate.

Various suitable distillation apparatuses can be used to carry out the distillation operation in each separation step and proceed in a continuous or discontinuous manner (batch). However, care should be taken to avoid overheating the rhodium complex. It is also very important to keep the high vacuum in the second distillation step to lower the concentration temperature to a minimum. It is therefore desirable to complete the distillation with the shortest residence time at the lowest temperature in order to obtain the required rhodium concentration. It is a matter of course that the components of the waste hydroformylation medium distilled according to the present invention cannot arbitrarily determine the longest or shortest residence time in practice of the present invention because their type and concentration change depending on the hydroformylation reaction. to be. Therefore, in such cases it is desirable to use a thin film evaporator, such as a wiped-film evaporator, which in most cases has a residence time of less than 10 minutes and preferably less than about 3 minutes at elevated temperatures. Because it is suitable for. In contrast, the residence time of a kettle type batch in the second stage distillation is several hours. However, in the first stage distillation, a betcher is suitable because it separates most of the volatile (low boiling point) substances in the waste medium, since the distillation proceeds at a pressure far higher and lower than the pressure applied in the second distillation stage. to be. In general, these two distillation steps are preferably carried out in thin film evaporators, in particular in wiped film evaporators. Such evaporators are well known and further explanation is omitted here. It should also be noted that, of course, each distillation step can be repeated more than once. That is, it must be repeated until the desired amount of volatiles have been removed or the required rhodium concentration has been obtained. In fact, when the thin film type evaporator is used, the residence time is short, so it is generally preferable to repeat the second stage distillation operation at least twice, thereby increasing the concentration of the rhodium complex concentrate required in steps. Will have

It should be noted that the rhodium reactivation in the partially deactivated catalyst present in the concentrated hydroformylation reaction medium concentrated in the present invention is not simply obtained by distilling the catalyst inhibitor from the rhodium catalyst. The basic change in the rhodium form of the partially deactivated catalyst occurs during the concentration process used in the present invention, that is, the rhodium form in the rhodium complex concentrate prepared by the concentration process of the present invention is partially deactivated rhodium complex. The particle size is generally larger than that of the rhodium in the catalyst, and the resulting rhodium complex concentrate is dark brown and mainly contains rhodium and a small amount of triarylphosphine (typically less than 10% by weight of the total weight of the concentrate). The remainder is a highly viscous rhodium complex medium consisting of high boiling point aldehyde condensation products and phosphine oxides produced in-house during the hydroformylation reaction from which the waste hard hydroformylation medium starting material is obtained.

It is a surprising finding that the rhodium complex concentrate prepared according to the present invention can be used as a reactivation rhodium source of rhodium complex catalyst in hydroformylation reaction. In fact, in the hydroformylation reaction using such a rhodium complex concentrate as a source of rhodium as a process catalyst, the reaction rate of the rhodium complex catalyst was obtained by using a waste hydroformylation reaction medium containing the partial deactivation catalyst derived from the concentrate as it is. It was found to be greater than one reaction rate.

The addition of an oxidizing agent such as oxygen or organic peroxide to the rhodium complex concentrate prepared according to the present invention can further improve the regeneration activity of the concentrate, and when the concentrate treated with the oxidant is used as the rhodium source of the hydroformylation reaction catalyst, It is particularly surprising that a significant improvement in hydroformylation activity can be achieved compared with the use of a waste hydroformylation reaction medium containing the partial deactivation catalyst from which the concentrate is derived, or if the concentrate is used without treatment with an oxidizing agent. It is a discovery.

It is difficult to explain the exact reason why the concentrate can be contacted with an oxidant to improve this regeneration activity. Whatever the reason, however, the oxidant has been found to convert large rhodium masses obtained in the preparation of the concentrate according to the invention into smaller catalytic rhodium particles which are commonly found in highly active and effective hydroformylation reactions. It is believed to play a facilitating role. This fact can also be explained by the fact that the concentrate color changes from dark brown to yellow with respect to the highly active rhodium complex catalyst during this hydroformylation reaction.

The oxidizing agent used in the present invention for the treatment of the rhodium complex concentrate may be selected from the group consisting of oxygen and organic peroxides, which are good in both a gaseous phase and a liquid phase. That is, an acidic or organic peroxide can be used as the oxidant. While preferred oxidants are oxygen, it is not necessary to use pure ones, and it is noted that it is more convenient and preferred to use them as a mixture with an inert gas such as nitrogen to minimize the risk of air or explosion. Indeed oxygen in the form of air is the most preferred and convenient oxidant. It may also be further diluted with an inert gas such as nitrogen in order to reduce the oxygen content if the operating conditions require stability precautions. Liquid organic peroxides that can be used as oxidants in the present invention include organic peroxides of the general formula ROO-R ', wherein R is a carboxylity of 2 to 20 carbon atoms, a monovalent hydrocarbon radical of 2 to 20 carbon atoms. Radicals selected from the group consisting of acyl radicals, aroyl radicals of 7 to 20 carbon atoms, alkoxycarbonyl radicals of 2 to 20 carbon atoms, and cycloalkoxy carbonyl radicals of 4 to 40 carbon atoms, and R 'means radicals selected from the group consisting of radicals defined in R and hydrogen. Preferred monovalent hydrocarbon radicals represented by R and R 'include alkyl and aralkyl radicals, in particular t-alkyl radicals of 4 to 20 carbon atoms and aralkyl radicals of 8 to 15 carbon atoms. Most preferred R 'is hydrogen (-H). Organic peroxides that can be used include t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide and the like. Such organic peroxides and methods for their preparation are well known in the art, with the most preferred organic peroxides being t-butylhydroperoxide.

In addition, by adding the oxidizing agent to the concentrate in the most convenient and suitable manner, it is another advantage that it is possible to achieve an improvement in the regeneration activity of the rhodium complex concentrate according to the oxidizer treatment. In this way, the method of treating the concentrate with the oxidizing agent is not determined, but it is possible by simply adding an amount of the oxidizing agent to the concentrate in an amount sufficient to improve the required concentration regeneration activity. For example, a gaseous or liquid oxidant may be added by concentrating the spent hydroformylation medium in the presence of an oxidant, or may be added during or after the concentrate is collected. In fact, the liquid organic peroxide may be added to the waste hydroformylation medium prior to the concentration process or may be added to the concentrate in the harvest or to the finished concentrate. Similarly, oxygen may more preferably be blown into the concentrate, which has been collected, collected or is still in film form on the thin film evaporator base wall. The concentrate can also be shaken or stirred to create a vortex to allow air to flow into the concentrate from the top. Alternatively, the regeneration activity of the concentrate may be improved by atomizing or atomizing the concentrate in air or by diffusing air into the concentrate during or after concentration. However, because oxygen is the more preferred oxidant and the rate of air diffusion is very slow in viscous concentrates, the best results are obtained by supplying air directly to the concentrates which are generally collected or still in film form in the thin film evaporator walls. Or a method of dispersing air through the concentrate, such as by stirring the concentrate to blow air from the top. In a method of adding the oxidant directly to the concentrate as a particularly preferred oxidant treatment, it should be noted that the viscous concentrate, if necessary, should first be diluted with a suitable solvent prior to the oxidant treatment to facilitate handling.

The oxidant treatment used in the present invention was designed to obtain improved regeneration activity than the activity of rhodium complex concentrates which had not been subjected to such oxidant treatments and the composition of the concentrates could be varied in their kind and concentration. It is obvious that certain values for conditions such as amount and partial pressure (concentration), temperature and oxidant treatment time cannot be imparted arbitrarily. Such broadly variable conditions are not of great importance, at least they are sufficient to achieve the required improvements. For example, the amount of added oxidant may only be an amount sufficient to obtain an improved regeneration activity than that of the rhodium complex concentrate which has not been subjected to an oxidizer treatment. In particular, there is no upper limit to the maximum amount of oxidant that can be used, but it may have a detrimental effect on hydroformylation reactions that are overexploitable due to high concentrations or oxygen, or that use rhodium complex concentrates as catalyst sources for rhodium. Excessive amounts of excess should not be used (e.g. excess of residual oil peroxide may be detrimental to phosphine ligands in hydroformylation reactions). Thus in some cases a small amount of oxidant may be more beneficial while under other conditions it may be more desirable to use a large amount of oxidant. In some situations, for example, only a small amount of oxidant may be used, while in some cases it may be more desirable to reduce the contact time by using a high concentration, ie a large amount of oxidant. Therefore, treatment conditions such as temperature, partial pressure (concentration), and contact time vary greatly depending on the oxidizing agent and treatment method, and the like, and accordingly, in the present invention, such conditions may be appropriately combined. For example, the reduction of any one of these conditions can be offset by increasing one or the other two of the other conditions, and vice versa. Generally the oxidant is added to the concentrate at a solution temperature of 0 ° to about 250 ° C., but in most cases an ambient to about 175 ° C. temperature is suitable. Moreover, the oxygen partial pressure should be 10 ^-4 to 10 atm in most cases, but the organic peroxide can be easily added to the concentrate at atmospheric pressure. The contact time, of course, is directly related to conditions such as temperature and oxidant concentration and can be from seconds or minutes to hours. If the concentrate is present as a thin film on the evaporator hot-air wall during the condensation process, the condensation with air requires very low oxygen partial pressures and only a few seconds of contact time due to the high temperatures used in the process. In contrast, when a large amount of concentrate is treated at normal oxygen partial pressure (10 ^-3 to 1 atm) at ambient or ambient temperature, several hours or more of contact time is required.

Therefore, as described above, the selection of the optimal level of these variables depends on the experience of the relevant oxidizer treatment process, and requires some experimental measurements to identify the optimal conditions in a given state. However, one of the benefits that may be included in such an oxidant treatment process used in the present invention is that the range of choices for the combination of reaction conditions most closely coupled to attain or at least close to the required specific results or requirements are required. It is wide.

Of course, when the oxidant treatment of the present invention is carried out again, care must be taken to select a reaction condition that can exclude the explosion hazard caused by high oxygen concentration in a limited space.

The ultimate object of the present invention is to prepare a rhodium complex concentrate having a regenerative activity and to use it as a source of rhodium for the hydroformylation reaction catalyst. Further, the more preferred rhodium complex concentrate of the present invention is hydroformylated at a reaction rate that can reach at least 50%, and most preferably at least 70%, of the reaction rate that can be obtained using the new rhodium complex catalyst when used. It should be possible to proceed with the reaction.

As described above, the regeneration activity of the rhodium complex concentrate prepared according to the present invention is a novel method using the reaction rate of the rhodium complex catalyst in the above reaction using the rhodium complex concentrate as the rhodium source for the hydroformylation catalyst. It can be determined by measuring the rhodium complex catalytic activity. This can easily be determined by running the hydroformylation reaction and continuously tracking the hydroformylation rate. The difference in hydroformylation rate (or difference in catalytic activity) can also be measured in a simple laboratory time range.

Therefore, the most preferred rhodium complex concentrate of the present invention uses it as a source of rhodium for the rhodium-triphenylphosphine complex catalyst, and the propylene: carbon monoxide: hydrogen molar ratio of about 1: 1: 1 and total pressure at about 100 ° C Rhodium dicarbonylacetylacetone ate as a source of rhodium for the rhodium-triphenylphosphine complex catalyst from the hydroformylation of propylene proceeded in the presence of the catalyst and free triarylphosphine using a gas mixture of about 75 psi Is an oxidizing agent-treated concentrate capable of producing butylaldehyde at a production rate corresponding to at least 50% more preferably at least 70% of the butylaldehyde production rate obtained by hydroformyl reaction under the same conditions.

Rhodium can be reactivated as described above, and Rhodium carbonyltriphenylphosphineacetylacetoneate, Rh ₂ O ₃ , Rh ₄ (CO) ₁₂ , Rh ₆ (CO) ₁₆ Rh (NO ₃ ) ₃ Rhodium complex concentrates may be used in the same manner as in the prior art for conventional catalyst precursors such as rhodium dicarbonylacetylacetoneate and the like. Therefore, it is not necessary to clarify in the present invention the particular manner in which this rhodium complex concentrate is used as the rhodium source of the rhodium complex catalyst for the hydroformylation reaction.

For example, the rhodium complex concentrate prepared according to the present invention is, by itself, a commonly known hydroformylation reaction for producing aldehydes (a prior art process as mentioned above) and has already been used to some extent. Rhodium complex catalysts (including catalysts prepared preliminarily according to conventional preparations or self-generated catalysts from conventional precursors as mentioned in the prior art described above or catalysts derived from rhodium complex concentrates prepared according to the invention) ) At least partially deactivated, acts as a catalyst to increase the reaction rate. By adding a small amount of the rhodium complex concentrate to the waste hydroformylation reaction medium of such hydroformylation reaction, it acts as an active rhodium source for the formation of additional rhodium complex catalyst in itself. Will increase the reaction rate. Rhodium complex concentrates used as such are of course required only in an amount sufficient to increase catalytic activity compared to prior addition of the concentrate to the spent hydroformylation reaction medium.

Moreover, the rhodium complex concentrate of the present invention is particularly suitable for use as a primary source of rhodium for rhodium complex catalysts formed in hydroformylation reactions. The preparation of the hydroformylation reaction medium using this rhodium complex concentrate as a base catalyst precursor can be made in any way, since this preparation method is not a limiting factor of the present invention. However, it is generally preferred to first dilute the medium consisting of rhodium complex concentrate and triarylphosphine to produce a hydroformylation medium that maintains the rhodium and triarylphosphine concentrations typically required in hydroformylation reactions. .

Thus, the rhodium complex concentrate is preferably mixed with a sufficient amount of solvent for the complex and a sufficient amount of triarylphosphine so that the medium can be composed of a solubilized rhodium complex and free triarylphosphine to prepare a hydroformylation medium. Wherein the amount of free triarylphosphine present is at least about 10 moles, preferably at least about 50 moles, more preferably at least about 100 moles per mole of rhodium present, and also the containing lodi of the medium. The amount is about 25 to about 1000 ppm, preferably about 50 to about 400 ppm, in terms of free metal rhodium.

Such a process of diluting the rhodium complex concentrate with triarylphosphine and a solvent to produce a hydroformylation medium can be easily proceeded by simply mixing the components according to a suitable method and sequence. In general, however, it is preferable to prepare a solution of triarylphosphine and a solvent and then add viscous rhodium complex concentrate to the solution.

Of course, since the purpose of preparing the hydroformylation medium of the present invention is for use in the hydroformylation reaction to prepare aldehydes from olefins as described above, the amount of constituents contained therein can be used to prepare such hydroformylation medium. The triarylphosphine and the solvent that can be used may be any triarylphosphine, solvent and amount applicable to the hydroformylation reaction.

For example, the amount of rhodium complex concentrate used to prepare the waste hydroformylation medium is only used to form the rhodium concentration (about 25 ppm to about 1000 ppm, preferably about 50 ppm to about 400 ppm) needed in the medium. It is the minimum amount required and the amount containing the minimum amount of rhodium catalyst necessary to promote the specific hydroformylation reaction required.

Similarly, triarylphosphines in the novel hydroformylation medium of the present invention, whether complex or free with rhodium, can be used in hydroformylation reactions as in the reactions and triaryl phosphines described above. Any aryl phosphine can of course be used. Preferred triarylphosphines are triphenylphosphines. At least a portion of the triarylphosphine used to prepare the novel hydroformylation medium of the present invention is, if necessary, distilled from the waste hydroformylation medium during rhodium complex concentrate production and recovered from the distillate by a suitable method. Arylphosphine can be used. This recovered triarylphosphine does not need to be purified and used in pure form and is used as a mixture with other compounds that do not interfere with catalytic activity or selectivity. The amount of triarylphosphine present in this medium is from about 0.5% to 40% by weight or more based on the total weight of the hydroformylation medium and as described above, the preferred content is rhodium in the hydroformylation medium. It is an amount sufficient to provide at least 10 moles, preferably at least about 50 moles, and more preferably at least about 100 moles of free triarylphosphine per mole. The upper limit of the amount of free triarylphosphine is not particularly limited, but is mainly limited by commercial and economical viewpoints.

From the same point of view, any solvent that can be used in the hydroformylation reaction described above as well as the solvent for the rhodium complex concentrate used to prepare the novel hydroformylation medium of the present invention can be used. Such solvents include the solvents described in US Pat. No. 3,527,809 and more preferably are the aldehyde products (e.g., n-butyraldehyde) prepared by this hydroformylation reaction and the corresponding aldehydes and / or as described above. Likewise high boiling point aldehyde condensation products corresponding to high boiling point aldehyde condensation products (e.g., butyraldehyde trimers) produced in-house during the hydroformylation reaction.

The hydroformylation reaction carried out in this aldehyde product solvent starts producing a high boiling aldehyde condensation product immediately during the reaction period so that such condensation product can be prepared and used if necessary. The use of such solvents, as well as the hydrolysis of the specific rhodium concentration required by this medium, as described above, as well as the specific hydro needed (such as rhodium complex concentrate and triarylphosphine) An amount sufficient to supply at least a basic amount of the rhodium catalyst necessary to promote the formylation reaction is sufficient. Generally the amount of this solvent may be from about 5% to about 95% by weight or more based on the total weight of the hydroformylation medium.

The above-mentioned reactivated novel hydroformylation medium of the present invention is washed with water or more preferably an aqueous alkaline solution before use in the hydroformylation reaction, thereby using a reactivated hydroformylation medium which has not been subjected to such a wash. It is a particularly surprising finding that the activation rate has been increased more than the hydroformylation activity rate obtained by the method. Unlike US Pat. No. 3,555,098, the present invention states that such a washing process is not used for the purpose of extracting the hindered acid that may accumulate during the hydroformylation reaction. The washing process as used herein facilitates the transformation of at least a portion of the large rhodium particles in the recycled rhodium complex concentrate to the catalytically more active small rhodium particles for reasons unknown at this time. As a result, the rate was obviously increased as compared with the hydroformylation rate obtained using this catalyst.

Thus, in general, this novel hydroformylation medium is preferably washed with water or, more preferably, with an aqueous alkaline solution before use in the hydroformylation reaction. This washing process is simply performed by washing the obtained new hydroformylation medium with water or alkaline aqueous solution, leaving the mixture until separated into two liquid phases, and then separating the aqueous layer from the washed non-aqueous hydroformylation medium layer. .

Alkaline materials suitable for the production of alkaline aqueous solutions include sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, alkali metals such as barium hydroxide, calcium hydroxide, aluminum hydroxide, hydroxides and carbonates of alkali metals and ammonium. The alkaline concentration of the aqueous wash solution may vary up to the solubility of the particular alkaline used. The alkaline material is preferably used as an aqueous solution containing about 0.1 to about 10% by weight alkaline material. More preferred alkaline aqueous solution is about 5 to 10% by weight sodium bicarbonate solution.

The washing is accomplished by simply mixing the hydroformylation medium with alkaline aqueous solution to be treated. This washing is carried out in air or nitrogen under atmospheric pressure or pressure and at a temperature of 25 ° C. to about 100 ° C. and preferably at atmospheric pressure and about 25 to 65 ° C. The washing is usually completed within a few minutes or 1 to 10 minutes and the amount of washing medium used is not critical but is used in the range of about 0.1 to about 1 part by volume in parts per hydroformylation medium to be treated. In general, it is most preferable to wash the hydroformylation medium to about 0.1 to 0.5 parts by volume of about 5% by weight aqueous sodium bicarbonate solution. In particular, if the hydroformylation medium is washed with an aqueous alkaline solution and the alkaline aqueous solution is separated (preferably preferred), then the hydroformylation medium is washed with water at least once, followed by residual excess of the basic compound used in the initial alkaline washing. Can be removed. Of course, the water used for such subsequent washing must be separated before the hydroformylation medium is used in the hydroformylation reaction, which is possible by simple phase separation as described above.

As described above, the present invention relates to an improved process for producing aldehydes by hydroformylating olefins with hydrogen and carbon monoxide in the presence of at least 10 moles of free triarylphosphine per mole of soluble rhodium complex catalyst and catalytically active rhodium. The improvement is characterized by the use of rhodium complex concentrate prepared from the waste hydroformylation reaction medium by the above-described method as the source of rhodium for the catalyst.

The present invention relates to a hydroformylation reaction. As described above, the rhodium complex concentrate may be used as a rhodium source for the rhodium complex catalyst by using any method, if necessary, and the reaction conditions of such a hydroformylation reaction may be It is not an important requirement of the present invention and this is well known as already described above. Preferred hydroformylation reactions are described in US Pat. Nos. 3,527,809 and US Pat. Nos. 762,335 and 776,934.

This hydroformylation reaction is carried out by reacting olefins with hydrogen and carbon monoxide gas in a liquid reaction medium containing at least 10 moles of free triarylphosphine per mole of soluble rhodium complex catalyst and catalytically active rhodium, preferably their normal isomers. Production of aldehydes rich in water and the reaction conditions in this reaction are essentially (1) a temperature of about 50 ° C to 145 ° C, preferably about 90 ° C to about 120 ° C, and (2) less than about 1500psia, preferably Total gas pressure of hydrogen, carbon monoxide and olefins of less than about 400 psia and more preferably less than about 350 psia, (3) a carbon monoxide partial pressure of less than about 100 psia, preferably from about 1 to about 50 psia, and (4) less than about 400 psia, preferably about It is characterized by a hydrogen partial pressure of 20 to about 200 psia. It is particularly preferred if the amount of free triarylphosphine generally present is at least about 50 moles and more preferably at least about 100 moles per mole of catalytically activedium.

The olefins hydroformylated according to the inventive process are well known in the art and contain 2 to 20 carbon atoms. Alphaolefins generally having 2 to 20 carbon atoms are more preferably hydroolefins containing alpha olefins having 2 to 6 carbon atoms such as ethylene, propylene, 1-butylene, 1-pentylene, 1-hexylene and the like. It is preferable to carry out a milling reaction. The olefins used in the inventive process may be linear or branched and may contain groups or substituents which do not significantly interfere with the hydroformylation reaction as described generally in the prior art, in particular US Pat. No. 3,527,809. The inventive process is particularly beneficial for hydroformylation of propylene to produce butyraldehydes with a high ratio of normal isomers to isomers.

The triarylphosphines used in the hydroformylation reaction of the present invention are well known as described above, and examples of the use of such triarylphosphines are described above. Most preferred triarylphosphine is triphenylphosphine.

The rhodium complex catalyst for the hydroformylation reaction of the present invention may include all the rhodium complex catalyst using the rhodium complex concentrate prepared from the waste hydroformylation reaction medium as a source of rhodium for the catalyst as described above. The method using this rhodium complex concentrate as a source of rhodium for a catalyst was mentioned above. As discussed in the above prior art, the active rhodium complex catalyst may be prepared in advance from the rhodium complex concentrate used in the present invention but is generally formed in the reaction medium under hydroformylation conditions. Thus, as in the case of the prior art described above, it can be said that the rhodium composite catalyst is mainly composed of carbon monoxide and triarylphosphine. Of course, as already explained above, the clue to "consisting mainly of" in the catalyst definition, whether added externally or generated by itself, is intended to exclude hydrogen complexed with rhodium as well as rhodium complexed alkylsubstituted phosphines in the reaction medium. Rather, it is meant to be inclusive rather than intentional.

The hydroformylation reaction of the present invention is preferably reacted in a liquid phase in a reaction zone containing a rhodium complex catalyst and a high boiling liquid aldehyde condensation product as described in the prior art and described above as a solvent.

It is also generally preferred to proceed the hydroformylation reaction of the present invention in a continuous manner, in particular in a continuous formulation employing the gas recirculation technique described above in US Pat. Nos. 762,335 and 776,934. Gas recirculation supplies a gaseous recycle stream consisting of at least hydrogen and unreacted olefins to the liquid phase reaction medium and to supply replenishment amounts of carbon monoxide, hydrogen and olefins to the liquid phase reaction medium, while unreacted olefins and hydrogen vapors from the liquid phase reaction medium. Separating a gaseous mixture consisting of a aldehyde product and a vaporized high boiling point condensation product of this aldehyde and recovering the aldehyde and its condensation product from the gaseous mixture to form a gaseous recycle stream, wherein the vaporized aldehyde condensation The product is removed from the liquid phase reaction medium at about the same rate as its rate of formation in the liquid phase reaction medium and transferred to the gaseous mixture to maintain a substantially constant amount of liquid phase reaction medium.

The hydroformylation reaction of the present invention is, of course, in the presence of similar additives which have been produced in-house in the hydroformylation reaction, such as alkyl-substituted phosphines, which have been added externally or for certain purposes, or are already described above and well known in the prior art. May proceed.

In particular, the content of the individual components of the various substances used in the hydroformylation reaction of the present invention is not very important in the production method of the present invention and their general and preferred amounts of use are already described above and can be easily determined from the aforementioned prior art.

Finally, the hydroformylation aldehyde product of the present invention has a wide range of uses, as mentioned in the prior art and well known, for example, which is particularly advantageous as a starting material for alcohol production.

All parts, percentages, and ratios mentioned in the examples and the appended claims are by weight unless otherwise indicated.

Example 1

Propylene is obtained by the continuous hydroformylation reaction with carbon monoxide and hydrogen in the presence of a rhodium complex catalyst consisting mainly of rhodium and free triphenylphosphine complexed with carbon monoxide and triphenylphosphine to produce butyraldehyde. In addition, a goose-neck condenser and vacuum pump were installed to etch about 8736 g of waste hydroformylation reaction medium containing less than 400 ppm of rhodium and its catalytic activity dropped to about 30% of the new catalyst activity. An external heating 12i distillation flask connected to was used. After filling the flask with waste reaction medium, the flask pressure is gradually reduced to about 100 mmHg. The waste reaction medium was heated to distill at a temperature of about 24 ° C. to about 153 ° C. and further reduced pressure was maintained at about 0.5 mm Hg during this distillation period. After 7 hours, about 4373 g of distillate (low boiling point) consisting mainly of butyraldehyde and containing little rhodium was collected, and the residue in the flask consisted of about 4293 g of high boiling point of the distilled waste reaction medium. It contains almost all of the rhodium in the catalyst.

The distillation residue sample of the above-described betch distillate is further concentrated by continuing to evaporate in a glass wiped-film evaporator which is heated to about 230 to 237 ° C with an electric heating tape and operated at about 0.4 to 0.5 mmHg. Distillate with little rhodium in the charge sample is collected at the top and a highly viscous rhodium complex concentrate distillate is obtained at the bottom of the wiped film evaporator at a rate of 19.8 g per hour, the distillation residue being charged It consists of about 5749 ppm rhodium and about 7.5 wt% triphenylphosphine, which means almost all of the rhodium originally contained in the sample (about 99.4%), and the rest is almost the same as the high boiling point of triphenylphosphine oxide and aldehyde pentapolymer. It is composed of organic matter.

로 희석하여, 약 298ppm 로디움과 4.6중량% 트리페닐포스핀(로디움 몰당 유리 트리페닐포스핀 약 61몰)을 함유하는 용액을 제조한다. 이어 이 용액시료는 약 100℃의 교반 오토크레브 반응기내의 약 75psi의 일산화탄소, 수소 및 프로필렌 1 : 1 : 1 몰비율 상태에서 프로필렌의 하이드로포밀화를 촉진시키는 데 사용된다. 이 농축액을 촉매로 로디움원으로서 사용한 이 반응에서의 로디움 복합촉매의 활성은 동일 조건하에서 새로운 로디움 복합체 촉매활성과 비교하여 약 52%임이 측정되었다.About 15.6 g of this rhodium complex concentrate distillation residue obtained from the thin film evaporator was weighed about 260 g of texanol, which was a mixture of about 15 g of triphenylphosphine and butyraldehyde trimer.

Dilute with to prepare a solution containing about 298 ppm rhodium and 4.6 wt% triphenylphosphine (about 61 moles of free triphenylphosphine per mole of rhodium). This solution sample is then used to promote hydroformylation of propylene at about 75 psi of carbon monoxide, hydrogen and propylene 1: 1: 1 molar ratio in a stirred autoclave reactor at about 100 ° C. The activity of the rhodium complex catalyst in this reaction using this concentrate as a rhodium source as a catalyst was determined to be about 52% compared to the new rhodium complex catalytic activity under the same conditions.

Another sample of diluted rhodium complex concentrate prepared according to the method described above was washed with 5% by weight aqueous sodium bicarbonate solution and then washed, followed by drying before use in hydroformylation of propylene under the same conditions as described above. It was. In this case, it was confirmed that the activity of the rhodium complex catalyst was increased to about 81% compared to the new rhodium complex catalyst activity under the same conditions.

Example 2

400 ppm obtained from a continuous hydroformylation reaction in which propylene is reacted with carbon monoxide and hydrogen to produce butyraldehyde in the presence of a rhodium complex catalyst consisting mainly of carbon monoxide and triphenylphosphine and a rhodium complex catalyst consisting of free triphenylphosphine About 4450 g of waste hydroformylation medium sample containing less than rhodium and its catalytic activity dropped to about 30% of the new catalytic activity was heated with electric heating tape to about 160 to 175 ° C and the pressure was about 7 to Evaporate in a glass wiped film evaporator maintained at 10 mmHg. Distillate, which contains little or no rhodium, consisting mainly of butyraldehyde and other low boilers, is collected at a rate of 128 g per hour. In addition, a total weight of about 3567 g of evaporated residue, consisting of the high boiling point material of the distilled waste medium and almost the entire amount of rhodium in the charged sample, is also collected at a rate of about 526 g per hour at the bottom of the evaporator.

This distillation residue obtained as described above is secondarily passed through an evaporator which is heated to about 233 to 242 ° C. and operated at about 0.5 to 1.2 mm Hg to further concentrate the residue. Almost no rhodium-containing distillate is collected from the top, and in addition to this, a high viscosity rhodium complex concentrate distillate is obtained from the bottom of the wiped film evaporator, which is at least 99.9% of the rhodium contained in the charged residue. It consists of about 13,227ppm rhodium and less than 5% of triphenylphosphine, the remainder is mainly a high boiling organic material such as triphenylphosphine oxide and aldehyde pentapolymer.

로 희석하여 약 328ppm 로디움과 약 5중량% 트리페닐포스핀(로디움 몰당 유리트리페닐포스핀 약 60몰)을 함유하는 용액을 제조한다. 이어 이 용액시료는 약 100℃의 교반 오토크래브 반응기내의 약 75psi의 일산화탄소, 수소 및 프로필렌 1 : 1 : 1몰 비율 상태에서 프로필렌의 하이드로포밀화를 촉진시키는 데 사용된다. 농출액을 촉매의 로디움 원으로서 사용한 이 반응에서의 로디움 복합촉매의 활성은 동일 조건하에서 새로운 로디움 복합체 촉매 활성과 비교하여 약 75%임이 측정되었다.Samples of rhodium complex enrichment distillate residue containing approximately 13,227 ppm rhodium were found to contain sufficient amounts of triphenylphosphine and texanol.

Dilution with to prepare a solution containing about 328 ppm rhodium and about 5 wt% triphenylphosphine (about 60 moles of free triphenylphosphine per mole of rhodium). This sample is then used to promote hydroformylation of propylene at about 75 psi of carbon monoxide, hydrogen and propylene 1: 1: 1 mol in a stirred autoclave reactor at about 100 ° C. The activity of the rhodium complex catalyst in this reaction using the concentrate as the rhodium source of the catalyst was determined to be about 75% compared to the new rhodium complex catalyst activity under the same conditions.

Another sample of the diluted rhodium complex concentrate prepared as described above was washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and then dried prior to use in the hydroformylation of propylene under the same conditions as described above. The activity of the rhodium complex catalyst in this case was found to increase by about 85% compared to the new rhodium complex activity under the same conditions.

Example 3

400 ppm obtained from a continuous hydroformylation reaction in which propylene is reacted with carbon monoxide and hydrogen to produce butyraldehyde in the presence of a rhodium complex catalyst consisting mainly of carbon monoxide and triphenylphosphine and a rhodium complex catalyst consisting of free triphenylphosphine For comparison of the waste hydroformylation reaction medium containing less than rhodium and its catalytic activity dropped to about 30% of the new catalytic activity, the Betch distillation was carried out at about 100 ° C. and about 10 mmHg, mainly for the low boiling point of the butyraldehyde product and the medium. The material was separated.

The distillation residue sample obtained in the distillation process is then used to promote hydroformylation of propylene at about 75 psi of carbon monoxide, hydrogen and propylene 1: 1: 1 molar ratio in a stirred autoclave reactor at about 100 ° C. In this reaction, the activity of the rhodium complex catalyst was determined to be about 29% compared to the new rhodium complex catalyst activity under the same condition.

Another sample of the distillation residue prepared as described above was washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and then dried prior to use in hydroformylation of propylene under the same conditions as described above. In this case, the activity of the rhodium complex catalyst was found to be about 34% compared to the activity of the new rhodium complex catalyst under the same conditions.

Example 4

400 ppm obtained from a continuous hydroformylation reaction in which propylene is reacted with carbon monoxide and hydrogen to produce butyraldehyde in the presence of a rhodium complex catalyst consisting mainly of carbon monoxide and triphenylphosphine and a rhodium complex catalyst consisting of free triphenylphosphine A 4 liter glass distillation vessel equipped with 20 tray columns was filled with about 4224 g of waste harddroformylated reaction medium containing less than rhodium and its catalytic activity dropped to about 23% of the new catalytic activity. Distillation was carried out at about 25 to about 185 ° C. and about 0.7 to 50 mm Hg. Rhodium free distillates consist mainly of mixtures of butyraldehyde and other low boilers.

About 85 g of the distillation residue was then charged to a high vacuum distillation apparatus equipped with a three stage oil diffusion pump and a mechanical vacuum pump, and the mechanical vacuum pump was operated to reduce the pressure to about 5 × 10 ⁻² mmHg. Then, the diffusion pump was operated to further reduce the pressure to about 5 × 10 ⁻⁵ to 6 × 10 ⁻⁵ mmHg, and heated with an electric heating tape to start distillation at about 50 ° C. and gradually increase the distillation temperature to about 93 ° C. . This isolated rhodium residue is mainly composed of butyraldehyde trimers, other high boiling butyl aldehyde condensation products, and triphenylphosphine. In addition, a rhodium complex concentrate residue is obtained, which contains about 2208 ppm rhodium and a small amount of triphenylphosphine (approximately 0.2 area% of gas chromatography analysis), which corresponds to more than 97% of rhodium in the charged waste medium. The remainder consists mainly of high-boiling organics such as triphenylphosphinic acid compounds and aldehyde pentapolymers.

로 회석시켜 약 303ppm 로디움과 약 5.3중량％ 트리페닐포스핀 (로디움 몰당 유리트리페닐포스핀 약 69몰)을 함유하는 약 50ml의 하이드로포밀화 용액을 제조한다. 이어 이 용액시료는 약 100℃의 교반오토크래브 반응기내의 약 75psi의 일산화탄소, 수소 및 프로필렌 1 : 1 : 1몰 비율상태에서 프로필렌의 하이드로포밀화를 촉진시키는데 사용된다. 상기 농축액을 촉매의 로디움 원으로서 사용한 반응에서의 로디움 복합체 촉매의 활성은 동일 조건하에서 새로운 로디움 복합체 촉매활성과 비교하여 약 39%임이 측정된다.The Rhodium complex concentrate residue sample thus obtained was obtained with a sufficient amount of triphenylphosphine and texanol.

Dilute with to prepare about 50 ml of hydroformylation solution containing about 303 ppm rhodium and about 5.3 wt% triphenylphosphine (about 69 moles of free triphenylphosphine per mole of rhodium). This sample is then used to promote hydroformylation of propylene at about 75 psi of carbon monoxide, hydrogen and propylene 1: 1: 1 in a stirred autoclave reactor. The activity of the rhodium complex catalyst in the reaction using the concentrate as the rhodium source of the catalyst is determined to be about 39% compared to the new rhodium complex catalytic activity under the same conditions.

Another sample of the dilute rhodium complex concentrate solution prepared as described above was washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and dried before use in the propylene hydroformylation reaction under the same conditions as described above. . In this case, the activity of the rhodium complex catalyst was found to increase by about 71% compared to the activity of the new rhodium complex catalyst under the same conditions.

Example 5

169 g of a sample containing almost no butyraldehyde obtained from the initial distillation step (25 to 185 ° C., 0.7 to 50 mmHg) of Example 4 was charged to a vacuum distillation apparatus equipped with a three-stage oil diffusion pump and a mechanical vacuum pump. do. The distillation proceeds at about 100 ° C. and about 5 × 10 ⁻⁵ mmHg, yielding about 147 g of distillate consisting mainly of about 36 ppm rhodium, butyraldehyde trimers, other high boiling butyraldehyde condensation products, and triphenylphosphine. To obtain. In addition, about 15 g of a high viscosity rhodium complex concentrated residue are also obtained, which contains about 3362 ppm rhodium and a small amount of triphenylphosphine, the remainder being mainly high boiling points such as triphenylphosphine oxide and aldehyde pentameric It consists of organic substances.

로 희석시켜 약 306ppm 로디움과 약 5.0중량% 트리페닐포스핀(로디움 몰당 유리트리페닐포시핀 약 64몰)을 함유하는 약 50ml의 하이드로포밀화 용액을 제조한다. 이어 이용액 시료는 약 100℃의 교반 오토크래브반응기 내에의 약 75psi의 일산화탄소, 수소 및 프로필렌 1 : 1 : 1몰 비율상태에서 프로필렌의 하이드로포밀화를 촉진시키는 데 사용된다. 이 농축액을 촉매의 로디움원으로서 사용한 반응에서의 로디움 복합체 촉매의 활성은 동일 조건하에서 새로운 로디움 복합체 촉매활성과 비교하여 약 49%임이 측정되었다.The rhodium complex concentrated residue sample thus obtained was obtained with a sufficient amount of triphenylphosphine and texanol.

Dilution with gives about 50 ml of hydroformylation solution containing about 306 ppm rhodium and about 5.0 weight percent triphenylphosphine (about 64 moles of free triphenylphosphine per mole of rhodium). The solution sample is then used to promote hydroformylation of propylene at about 75 psi of carbon monoxide, hydrogen and propylene 1: 1: 1 mol in a stirred autoclave reactor at about 100 ° C. The activity of the rhodium complex catalyst in the reaction using this concentrate as the rhodium source of the catalyst was determined to be about 49% compared to the new rhodium complex catalytic activity under the same conditions.

Another sample of the diluted rhodium complex concentrate prepared according to the method described above was washed with 5% by weight aqueous sodium bicarbonate solution, then washed with water and dried before use in the propylene hydroformylation reaction under the same conditions as described above. . In this case, the activity of the rhodium composite catalyst was found to increase by about 77% compared to the new rhodium composite catalyst activity under the same conditions.

Example 6

로 희석시켜 약 299ppm 로디움과 약 5.2중량% 트리페닐포스핀(로디움 몰당 유리 트리페닐포스핀 약 68몰)을 함유하는 약 50ml의 하이드로포밀화용액을 제조한다. 이어 이 용액시료는 약 100℃의 교반오토크래브 반응기 내의 약 75psi의 일산화탄소, 수소 및 프로필렌 1 : 1 : 1몰 비율상태에서 프로필렌의 하이드로포밀화를 촉진시키는 데 사용된다. 이 농축액을 촉매의 로디움원으로서 사용한 반응에서의 로디움 복합체 촉매활성은 동일 조건하에서 새로운 로디움 복합체 촉매활성과 비교하여 약 71%임이 측정되었다.400 ppm obtained from a continuous hydroformylation reaction in which propylene is reacted with carbon monoxide and hydrogen to produce butyraldehyde in the presence of a rhodium complex catalyst consisting primarily of carbon monoxide and triphenylphosphine and a rhodium complex catalyst consisting of free triphenylphosphine Waste hydroformylation reaction medium containing less than rhodium and having its catalytic activity lowered to about 30% of the new catalytic activity was charged to a Rotoevaporator and distilled under reduced pressure to obtain mainly butyraldehyde and other low boiling aldehydes. The condensation product is removed from this medium as distillate. 190 g of the residue containing almost no butyraldehyde obtained from the distillation was charged to a high vacuum distillation apparatus equipped with a three-stage oil diffusion pump and a mechanical vacuum pump, and after removing all residual butyaldehyde under ambient temperature and reduced pressure, The pressure is then further reduced to about 2.5 × 10 ⁻² mmHg. Run the diffusion pump and gradually raise the temperature to about 100 ° C at about 6x10 ^-5 mmHg. The distillation was stopped after about 48 hours, and the distillate thus separated was mainly composed of about 7 ppm rhodium, butyraldehyde trimer, other high boiling aldehyde condensation products, and triphenylphosphine. In addition, a high-viscosity rhodium complex concentrate residue is obtained, which contains about 4766 ppm rhodium and a small amount of triphenylphosphine, with the remainder consisting mainly of high-boiling organics such as triphenylphosphine oxide and aldehyde pentapolymer. The Rhodium complex concentrate residue sample thus obtained was obtained with a sufficient amount of triphenylphosphine and texanol.

Dilution with gives about 50 ml of hydroformylation solution containing about 299 ppm rhodium and about 5.2 wt% triphenylphosphine (about 68 moles of free triphenylphosphine per mole of rhodium). This solution sample is then used to promote hydroformylation of propylene at about 75 psi of carbon monoxide, hydrogen and propylene 1: 1: 1 molar ratio in a stirred autoclave reactor at about 100 ° C. It was determined that the rhodium complex catalytic activity in the reaction using this concentrate as the rhodium source of the catalyst was about 71% compared to the new rhodium complex catalytic activity under the same conditions.

Another sample of diluted rhodium complex concentrate prepared as described above was washed with 5% by weight aqueous sodium bicarbonate solution, washed with water and then dried before use in hydroformylation under the same conditions as described above. It is found that the rhodium complex catalytic activity in this case is increased to about 87% compared to the new rhodium complex catalytic activity under the same conditions.

Example 7

400 ppm obtained from a continuous hydroformylation reaction in which propylene is reacted with carbon monoxide and hydrogen to produce butyraldehyde in the presence of a rhodium complex catalyst consisting primarily of carbon monoxide and triphenylphosphine and a rhodium complex catalyst consisting of free triphenyl phosphine About 865 pounds of spent hydroformylation reaction medium containing less than rhodium and its catalytic activity down to about 30% of the new catalyst activity was charged to a standard wiped film evaporator at a charge rate of about 135 to about 322.5 pounds per hour. Oil-fired heating and distilled in this evaporator maintained at a temperature of about 207 to about 243 ° C. and about 100 to about 150 mmg. The distillate collected at the top consists mainly of a mixture of butyraldehyde products and other low boiling aldehyde condensation products, whereas the distillation residue obtained will contain almost all of the rhodium and triphenylphosphines contained in the waste feed medium.

The collected distillation residue is heated to a temperature of about 232 to about 290 ° C. at a charging rate of about 147.5 to about 281.3 pounds / hour, and reloaded to a wiped film evaporator under pressure of about 3.1 to about 6.0 mmHg to continue concentration. Free flowing fluid distillates, consisting mainly of butyraldehyde trimers, other high boiling aldehyde condensation products, and triphenylphosphine, are separated from the top. Along with this, a mixed residue containing about 912 ppm rhodium and consisting mainly of butyraldehyde trimers, other high boiling aldehyde condensation products, triphenylphosphine and triphenylphosphine oxides is obtained in the evaporator. Samples of the individual rhodium complex concentrated residues constituting the mixed residue were periodically collected and it was confirmed that the rhodium concentration of the residue sample ranged from about 1600 to about 2700 ppm. High Rhodium values were obtained for this sample because no sample was taken until the wiped film evaporator reached equilibrium.

로 희석하여 약 295ppm 로디움 및 약 5.0중량% 트리페닐포스핀(로디움 1몰당 트리페닐포스핀 약 67몰)을 함유하는 하이드로포밀화 용액을 제조하였다. 이어 이용액 시료는 약 100℃의 교반 오토크래브 반응기의 약 75psi의 일산화탄소, 수소 및 프로필렌 1 : 1 : 1몰 비율상태에서 프로필렌의 하이드로포밀화를 촉진시키는 데 사용하였다. 이 농축액을 촉매의 로디움 원으로 사용한 반응에서의 로디움 복합체 촉매활성은 동일 조건하에서 새로운 로디움 복합체 촉매활성과 비교하여 약 74%임이 확인되었다.Some of each of the resulting rhodium complex concentrates containing about 2665 ppm rhodium was charged with sufficient triphenylphosphine and texanol.

Dilution with gave a hydroformylation solution containing about 295 ppm rhodium and about 5.0 wt% triphenylphosphine (about 67 moles of triphenylphosphine per mole of rhodium). The solution sample was then used to promote hydroformylation of propylene at about 75 psi carbon monoxide, hydrogen and propylene 1: 1: 1 molar ratio in a stirred autoclave reactor at about 100 ° C. It was confirmed that the rhodium complex catalytic activity in the reaction using this concentrate as the rhodium source of the catalyst was about 74% compared to the new rhodium complex catalytic activity under the same conditions.

Another sample of the diluted rhodium complex concentrated solution prepared as described above was washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and dried prior to use in the hydroformylation reaction under the same conditions as described above. In this case, the rhodium complex catalytic activity was found to be about 67% compared to the new rhodium complex catalytic activity under the same conditions.

Example 8

The mixed residual product of Example 7 containing about 912 ppm rhodium was heated to a temperature of about 275 to 279 ° C. and about 117.5 to about 153.8 pounds / hour in a wiped film evaporator maintained at about 2.9 to 3.9 mmHg pressure. Reloading at charge rate continued to concentrate. Almost no rhodium-containing distillates, consisting mainly of butyraldehyde trimers, other high-boiling aldehyde condensation products and triphenylphosphine, are removed from the top and, in addition, contain almost all of the loading rhodium mainly The mixed residue, which consists of phenylphosphine oxide and higher boiling aldehyde condensation products (e.g. butyraldehyde pentahydrate), remains more concentrated in the evaporator than the charged material. Samples of the rhodium complex concentrated residue constituting the concentrated mixed residue were periodically collected, and the residue sample was confirmed to have a rhodium concentration in the range of about 6500 to about 11,600 ppm.

로 희석하여 약 340ppm 로디움 및 약 5.0중량% 트리페닐포스핀(로디움 1몰당 유리 트리페닐포스핀 약 58몰)을 함유하는 하이드로포밀화 용액을 제조하였다. 이어 이용액 시료는 약 100℃의 교반 오토크래브 반응기의 약 75psi의 일산화탄소, 수소 및 프로필렌 1 : 1 : 1몰 비율상태에서 프로필렌의 하이드로포밀화를 촉진시키는 데 사용하였다. 이 농축액을 촉매의 로디움원으로 사용한 반응에서의 로디움 복합체 촉매활성은 동일 조건하에서 새로운 로디움 복합체 촉매활성과 비교하여 약 76%임이 측정되었다.Some of the rhodium complex concentrates containing about 6481 ppm rhodium thus obtained were charged with sufficient triphenylphosphine and texanol.

Dilution with gave a hydroformylation solution containing about 340 ppm rhodium and about 5.0 wt% triphenylphosphine (about 58 moles of free triphenylphosphine per mole of rhodium). The solution sample was then used to promote hydroformylation of propylene at about 75 psi carbon monoxide, hydrogen and propylene 1: 1: 1 molar ratio in a stirred autoclave reactor at about 100 ° C. It was determined that the rhodium complex catalytic activity in the reaction using this concentrate as the rhodium source of the catalyst was about 76% compared to the new rhodium complex catalytic activity under the same conditions.

Another sample of the diluted rhodium complex concentrate prepared as described above was washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and then dried before use in the hydroformylation reaction under the same conditions as described above. In this case, the rhodium complex catalytic activity was found to be about 80% compared to the new rhodium complex catalytic activity under the same conditions.

Example 9

로 희석하여 약 326ppm 로디움과 약 5.0중량% 트리페닐포스핀(로디움 1몰당 유리트리페닐포스핀 약 68몰)을 함유하는 하이드로포밀화 용액을 제조하였다.A portion of the rhodium complex concentrate sample containing about 11588 ppm rhodium, obtained according to the method described in Example 8, was charged with sufficient amounts of triphenylphosphine and texanol.

Dilution with gave a hydroformylation solution containing about 326 ppm rhodium and about 5.0 wt% triphenylphosphine (about 68 moles of free triphenylphosphine per mole of rhodium).

A portion of the solution was then used to promote hydroformylation of propylene at about 75 psi of carbon monoxide, hydrogen, and propylene 1: 1: 1 molar ratio in a stirred oatcrab reactor at about 100 ° C. The activity of the rhodium complex catalyst in the reaction using this concentrate as the rhodium source of the catalyst was about 67% compared to the new rhodium complex catalytic activity under the same conditions.

Another sample of the diluted rhodium complex concentrate prepared as described above was washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and dried before use in hydroformylation under the same conditions as described above. In this case, the rhodium complex catalytic activity was found to be about 83% compared to the new rhodium complex catalytic activity under the same conditions.

Example 10

For the purpose of comparative experiments, the same waste hydroformylation reaction medium as used as the feedstock in Example 7 was used to produce propylene in a stirred autoclave reactor at about 100 ° C. with about 75 psi of carbon monoxide, hydrogen and propylene 1: 1: 1 molar ratio. Used to promote hydroformylation. The activity of the rhodium complex catalyst in this reaction was determined to be about 30% compared to the new rhodium complex catalyst activity under the same conditions.

Other samples of the waste hydroformylation reaction medium were washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and then dried prior to use in the hydroformylation reaction under the same conditions as described above. The rhodium composite catalytic activity in this case is about 40% compared to the new rhodium composite catalytic activity under the same conditions.

Example 11

과 혼합하여 약 211ppm 로디움과 약 12.3% 트리페닐포스핀(로디움 1몰당 유리 트리페닐포스핀 약 236몰)을 함유하는 하이드로포밀화 용액을 제조하였다. 이같이 제조한 하이드로포밀화 용액은 5중량% 중탄산나트륨 수용액으로 세척하고 이어 수세척한 후 건조하였다.17.3 g of a rhodium complex concentrate sample containing about 11588 ppm rhodium obtained according to the method described in Example 8 above was weighed with about 120 g of triphenylphosphine and about 862.7 g of texanol.

And a hydroformylation solution containing about 211 ppm rhodium and about 12.3% triphenylphosphine (about 236 moles of free triphenylphosphine per mole of rhodium). The hydroformylation solution thus prepared was washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and dried.

About 800 ml aliquots of the hydroformylation solution washed as described above were charged to a continuous gas recycle reactor and used to hydroformify propylene with carbon monoxide and hydrogen in a reactor having a total gas pressure of about 105 ° C. and about 230 psi. . After one day use, the hydroformylation reaction was about 71% compared to the rhodium complex catalytic activity. The rhodium complex catalytic activity of this hydroformylation reaction after one week of use was about 87% compared to the new rhodium complex catalytic activity after one week of use under the same conditions. The rhodium complex catalytic activity of the hydroformylation reaction after 17 days of use was about 85% compared to the new rhodium complex catalytic activity after 17 days of use under the same conditions.

Example 12

과 혼합하여 약 200ppm 로디움과 약 12중량 트리페닐포스핀(로디움 1몰당 유리 트리페닐포스핀 약 236몰)을 함유하는 하이드로포밀화 용액을 제조하였다. 이 하이드로포밀화 용액 약 20mi을 분취하여 연속 1회통과 반응기(continuous sinle-pass reactor)에 장입하고 약 105℃ 및 약 165psi의 총가스 압력을 갖는 반응기내에서 프로필렌을 일산화탄소 및 수소로 하이드로포밀화 시키는데 사용하였다. 1일 사용후 하이드로포밀화 반응의 로디움 복합체 촉매활성은 동일조건하에서 1일 사용한 후의 새로운 로디움 복합체 촉매활성과 비교하여 약 88%였다. 23일 사용후 이 하이드로포밀화 반응의 로디움 복합체 촉매활성은 동일 조건하에 23일 사용한 후의 새로운 로디움 복합체 촉매활성과 비교하여 거의 동일하였다.3.5 grams of a rhodium complex concentrate sample containing about 11588 ppm rhodium obtained according to the method described in Example 8, above, about 24 g triphenylphosphine and about 172.5 g texanol

And a hydroformylation solution containing about 200 ppm rhodium and about 12 weight triphenylphosphine (about 236 moles of free triphenylphosphine per mole of rhodium). About 20 mi of this hydroformylation solution is aliquoted and charged into a continuous sinle-pass reactor to hydroformyl propylene with carbon monoxide and hydrogen in a reactor having a total gas pressure of about 105 ° C. and about 165 psi. Used. The rhodium complex catalytic activity of the hydroformylation reaction after 1 day of use was about 88% compared to the new rhodium complex catalytic activity after 1 day of use under the same conditions. The rhodium complex catalytic activity of this hydroformylation reaction after 23 days of use was almost the same as that of the new rhodium complex catalyst activity after 23 days of use under the same conditions.

Other samples of the hydroformylation solution prepared as described above were washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and dried before use in the hydroformylation of propylene under the same conditions as described above. After 1 day of use, the rhodium complex catalyst had about 87% of the activity compared to the new rhodium complex catalyst activity used for 1 day under the same conditions. After 23 days of use, the rhodium composite catalyst was almost identical to the new rhodium composite catalyst activity used for 23 days under the same conditions.

Example 13

로 희석하여 약 230ppm 로디움과 약 5.0중량% 트리페닐포스핀(로디움 몰당 트리페닐포스핀 약 85몰)을 함유하는 하이드로포밀화 용액을 제조하였다.A portion of the rhodium complex concentrate sample containing about 2419 ppm rhodium obtained according to the method described in Example 7 above was charged with sufficient triphenylphosphine and texanol.

Dilution with gave a hydroformylation solution containing about 230 ppm rhodium and about 5.0 wt% triphenylphosphine (about 85 moles of triphenylphosphine per mole of rhodium).

A series of individual samples of this hydroformylation solution were washed with water or washed with a 5% by weight solution of various base materials, followed by washing with water to completely remove residual residues of the used base materials. Each washing solution was dried and then used to promote hydroformylation of propylene in a stirred autoclave reactor at about 100 ° C. in about 75 psi carbon monoxide, hydrogen and propylene 1: 1: 1 molar ratio. The relative activities of each sample solution before and after washing are described in Table I below. This is the relative activity of the sample solution activity as 1.00 before washing.

TABLE I

Example 14

로 희석하여 약 300ppm 로디움과 약 5중량% 트리페닐포스핀(로디움 1몰당 유리 트리페닐포스핀 약 66몰)을 함유하는 하이드로포밀화 용액을 제조하였다. 이같이 제조한 각 용액의 일부를 약 75psi의 일산화탄소, 수소 및 프로필렌 1 : 1 : 1몰 비율 상태의 약 100℃ 교반 오토크래브 반응기에서 프로필렌의 하이드로포밀화를 촉진시키는 데 사용하였다. 이같이 제조한 각개 용액의 다른 일부를 5중량% 중탄산나트륨 수용액으로 세척하고 이어 수세척한 후 상술한 바와 동일한 조건하에서 프로필렌의 하이드로포밀화에 사용하기 전에 건조하였다. 가열을 행하지 않은 로디움 복합체 농축물로부터 유도된 시료 용액의 활성도를 임의로 1.00으로 정하고 이에 대한 각시료 용액의 세척전 및 세척후 상대 활성도를 다음 표 Ⅱ에 기록하였다.A series of samples taken from one of the rhodium complex concentrate samples containing about 6481 ppm rhodium obtained according to the method described in Example 8 above was heated at about 160 ° C. for 2, 4, 8 and 16 minutes. The initial unheated sample of each of the concentrates and the individual heated samples were followed by sufficient triphenylphosphine and texanol.

Dilution with to prepare a hydroformylation solution containing about 300 ppm rhodium and about 5% by weight triphenylphosphine (about 66 moles of free triphenylphosphine per mole of rhodium). A portion of each solution thus prepared was used to promote hydroformylation of propylene in about 100 ° C. stirred autoclave reactor at about 75 psi carbon monoxide, hydrogen and propylene 1: 1: 1 molar ratio. Another portion of each solution thus prepared was washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and dried before use in hydroformylation of propylene under the same conditions as described above. The activity of the sample solution derived from the rhodium complex concentrate without heating was arbitrarily set to 1.00 and the relative activities before and after washing of the respective sample solutions were recorded in the following Table II.

TABLE II

The concentrates of Examples 2, 7-9, 11 and 12 were stored for 3 to 4 months in the presence of air prior to measuring activity, and the activity given in this example is based on their preparation period and / or their airborne organs. It is believed that during the exposure period, at least in part due to the air diffused in this concentrate, the concentrate prepared in the thin film evaporator according to the invention and tested on or immediately after the preparation is measured in the same way as a new rhodium This is because the activity is about 45 to 55% before washing and about 55 to 70% after washing as compared to the composite catalytic activity.

Example 15

400 ppm obtained from a continuous hydroformylation reaction in which propylene is reacted with carbon monoxide and hydrogen to produce butyraldehyde in the presence of a rhodium complex catalyst consisting primarily of carbon monoxide and triphenylphosphine and a rhodium complex catalyst consisting of free triphenylphosphine Arthur F. Smith, with an outer wall temperature of about 141 to 155 ° C and 0.4 to 0.25 mmHg, containing 655 g of waste hydroformylation reaction medium sample containing less than rhodium and whose catalytic activity is reduced to about 30% of the new catalytic activity. Concentrated in a thin film evaporator for the laboratory. The charging rate is about 546 g / hour, and about 153 g of almost no rhodium-containing distillate, consisting mainly of butyraldehyde and other low boilers, is collected at the top. The distillation residue of the first distillation, consisting of the high boiling point material of the distilled waste medium and almost all of the rhodium of the original waste charge sample, was collected again and collected at 244 to 251 ° C. and 0.3 mmHg evaporator at a charge rate of about 361 g / hour. Second distillation is carried out to further concentrate. About 492 g of distillate, which contains little rhodium, is collected at the top. In addition, a highly viscous rhodium complex concentrated distillation residue is collected at the bottom of the evaporator. The residue contains about 5672 ppm rhodium and a small amount of triphenylphosphine, and the remainder is mainly a high ratio such as triphenylphosphine oxide and aldehyde 5-containing It consists of a viscous organic substance.

로 희석시켜 약 300ppm 로디움과 약 5중량% 트리페닐포스핀(로디움 1몰당 유리 트리페닐포스핀 약 65몰)을 함유하는 갈색용액을 제조하였으며 또 이용액 시료는 이어 75psi일산화탄소, 수소 및 프로필렌이 1 : 1 : 1몰 비율 상태의 약 100℃ 교반 오토크래브 반응기에서 프로필렌의 하이드로포밀화를 촉진시키는 데 사용하였다. 이 농축액을 촉매의 로디움 원으로서 사용한 반응에서의 로디움 복합체 촉매활성은 동일 조건하에서 로디움 디카보닐 아세틸 아세톤에이트를 촉매의 로디움원으로 사용한 새로운 로디움 복합체 촉매활동과 비교하여 약 34%였다.On the day when the rhodium complex concentrated distillation residue containing about 5672 ppm rhodium was prepared, the concentrate sample was loaded with sufficient triphenylphosphine and sufficient texanol.

Was diluted to prepare a brown solution containing about 300 ppm rhodium and about 5% by weight triphenylphosphine (about 65 moles of free triphenylphosphine per mole of rhodium). The sample was followed by 75 psi carbon monoxide, hydrogen and propylene. It was used to promote hydroformylation of propylene in a about 100 ° C. stirred autoclave reactor in a 1: 1: 1 molar ratio. The rhodium complex catalytic activity in the reaction using this concentrate as the rhodium source of the catalyst was about 34% under the same conditions as the new rhodium complex catalytic activity using the rhodium dicarbonyl acetyl acetoneate as the rhodium source of the catalyst.

On the same day another sample of the diluted rhodium complex concentrate prepared as described above was washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and dried prior to use in hydroformylation of propylene under the same conditions as described above. do. In this case, the rhodium complex catalytic activity was found to increase by about 57% compared to the new rhodium complex catalytic activity under the same conditions.

Another sample of rhodium complex concentrate distillation residue containing about 5672 ppm rhodium prepared on the same day was given air over 64 hours at room temperature. The air-treated sample was then diluted according to the same method described above on the day the sample was prepared to give a light brown solution containing about 300 ppm rhodium and about 5 wt% triphenylphosphine and prepared from this air treated concentrate. The prepared solution sample was used to promote hydroformylation of propylene under the same conditions as described above. The activity of the rhodium catalyst using the air-treated concentrate as the rhodium source of the catalyst was about 62% compared to the new rhodium complex catalytic activity under the same conditions.

Another sample solution of the diluted air-treated rhodium complex concentrate prepared as described above was washed the same day with 5% aqueous sodium bicarbonate solution and then washed with water before use in the hydroformylation of propylene under the same conditions as described above. Dried. In this case, the rhodium complex catalytic activity was increased to about 82% compared to the new rhodium catalytic activity under uniform conditions.

For comparison, one sample of the original waste hydroformylation reaction medium (i.e., the charge material originally used in this example) was washed with aqueous sodium bicarbonate solution and water and dried as described above, and the other sample was not washed. , Hydroformylation of propylene under the same conditions as described above. The rhodium complex catalytic activity using the non-washed sample of the waste hydroformylated medium as the source of the catalyst was about 30% compared to the new rhodium complexed catalyst activity, while the washed sample of the spent hydroformylated medium was used as the source of the catalyst. The rhodium complex catalytic activity used was about 33% compared to the new rhodium complex catalytic activity.

Example 16

400 ppm obtained from a continuous hydroformylation reaction in which propylene is reacted with carbon monoxide and hydrogen to produce butyraldehyde in the presence of a rhodium complex catalyst consisting mainly of carbon monoxide and triphenylphosphine and a rhodium complex catalyst consisting of free triphenylphosphine Arthur F. Smith laboratory thin film containing less than rhodium and whose catalytic activity was lowered to about 32% of the new catalytic activity was sampled at 476 g of the waste hydroformylation reaction medium at an external wall temperature of about 150 ° C. and operated at about 3 mmHg. Concentrated in a formula evaporator. The waste medium is charged over 90 minutes and approximately 385 g of distillation residue is collected, which contains the high boiling point material of the waste medium and almost all the rhodium of the original waste charge sample. About 337 g of this primary distillate was further concentrated by secondary distillation at about 230 to 245 ° C. and 3 mm Hg evaporator for 2 hours, containing about 6739 ppm rhodium and a small amount of triphenylphosphine, the remainder being mainly triphenyl A high viscosity rhodium complex concentrate distillation residue consisting of high boiling organic materials such as phosphine oxide and aldehyde pentapolymer is obtained.

로 희석시켜 약 300ppm 로디움과 약 5중량% 트리페닐포스핀(로디움 1몰당 유리트리페닐포스핀 약 65몰)을 함유하는 용액을 제조하였으며, 이용액 시료는 이어 약 75psi의 일산화탄소, 수소 및 프로필렌이 1 : 1 : 1몰 비율상태의 약 100℃ 교반 오토크래브 반응기에서 프로필렌의 하이드로포밀화를 촉진시키는 데 사용하였다. 이 농축액을 촉매의 로디움원으로 사용한 반응에서의 로디움 복합체 촉매활성은 동일 조건하에서 로디움 디카보닐 아세틸 아세톤 에이트를 촉매의 로디움원으로 사용한 새로운 로디움 복합체 촉매활성과 비교하여 약 46%였다.On the day the rhodium complex concentrate distillation residue containing about 6739 ppm rhodium was made, concentrate the sample with sufficient triphenylphosphine and sufficient texanol.

A solution containing about 300 ppm rhodium and about 5 wt% triphenylphosphine (about 65 moles of free triphenylphosphine per mole of rhodium) was prepared by diluting with a sample of about 75 psi of carbon monoxide, hydrogen, and propylene. This was used to promote the hydroformylation of propylene in a about 100 ° C. stirred autoclave reactor in a 1: 1 molar ratio. The rhodium complex catalytic activity in the reaction using this concentrate as the rhodium source of the catalyst was about 46% compared to the new rhodium complex catalytic activity using rhodium dicarbonyl acetyl acetoneate as the source of rhodium under the same conditions.

Another sample of the diluted rhodium complex concentrate prepared as described above on the same day was washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and then used for hydroformylation of propylene under the same conditions as described above. Dried. In this case, the rhodium complex catalytic activity was found to increase by about 58% compared to the new rhodium complex catalytic activity under the same conditions.

After two weeks another sample of the rhodium complex concentrate distillation residue containing about 6739 ppm rhodium was taken and passed through the air at 50 ° C. for 16 hours overnight. The air-treated sample was diluted in the same manner as described above to prepare a solution containing about 300 ppm rhodium and about 5 wt% triphenylphosphine, and described the solution sample prepared from the air-treated concentrate. It is used as a catalyst for hydroformylation of propylene under the same conditions. The activity of the rhodium catalyst using the air treatment concentrate as the rhodium source of the catalyst was about 75% compared to the new rhodium complex catalytic activity under the same conditions, and the diluted air treated rhodium composite prepared as described above on the same day The other sample solution of the concentrate was first washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and then dried prior to use in hydroformylation of propylene under the same conditions as described above. In this case, the rhodium complex catalytic activity increased by about 86% compared to the new rhodium complex catalytic activity under the same conditions.

For comparison, one sample of the original waste hydroformylation reaction medium (i.e. the charge material originally used in this example) was washed with sodium bicarbonate solution and water and dried as described above, and then the other sample was not washed. It was used for hydroformylation of propylene under the same conditions as described above. The activity of the rhodium complex catalyst using the non-washed sample of the waste hydroformylation medium as the source of the catalyst was about 32% compared to the activity of the new rhodium complex catalyst, while the washed sample of the waste hydroformylation medium was used as the roddy of the catalyst. The activity of the rhodium complex catalyst used as the source of um was about 40% compared to the new rhodium complex catalyst activity.

Example 17

400 ppm obtained from a continuous hydroformylation reaction in which propylene is reacted with carbon monoxide and hydrogen to produce butyraldehyde in the presence of a rhodium complex catalyst consisting primarily of carbon monoxide and triphenylphosphine and a rhodium complex catalyst consisting of free triphenylphosphine Arthur F. Smith experiments in which 627 g of waste hydroformylation reaction medium sample containing less than rhodium and having a catalytic activity lowered to about 30% of the new catalytic activity were operated at an outer wall temperature of about 139 to 152 ° C and operated at 0.7 to 0.8 mmHg. Concentrated on a practical thin film evaporator. The charge rate is about 482 g / hour and about 159 g of little rhodium-free distillate, consisting mainly of butyraldehyde and other low boiling materials, is obtained from the top. The first distillation residue and waste consisting of the high boiling point material of the waste medium used for the distillation and almost all of the rhodium of the original waste charge sample were collected and collected in the evaporator under conditions of 234 to 248 ° C., about 2.2 mmHg. While in the thin film on the hot wall, it is supplied through air with an evaporator to maintain pressure, and further concentrated by secondary distillation, containing about 10,692 ppm rhodium and a small amount of triphenylphosphine, with the remainder being mainly A highly viscous rhodium complex concentrate distillation residue consisting of high boiling organic materials such as triphenylphosphine oxide and aldehyde pentapolymer is obtained.

로 희석하여 약 330ppm 로디움과 약 5중량% 트리페닐포스핀(로디움 1몰당 유리 트리페닐포스핀 약 60몰)을 함유하는 용액을 제조하였으며, 이 용액시료는 이어 약 75psi의 일산화탄소, 수소 및 프로필렌이 1 : 1 : 1몰 비율 상태의 약 100℃ 교반 오토크래브 반응기에서 프로필렌의 하이드로포밀화를 촉진시키는 데 사용하였다. 이 농축액을 촉매의 로디움원으로 사용한 반응에서 로디움 복합체 촉매활성은 동일 조건하에서 로디움 디카보닐 아세틸 아세톤에이트를 촉매의 로디움원으로 사용한 새로운 로디움 복합체 촉매활성과 비교하여 약 39%였다.Five days after the air-treated rhodium complex concentrate distillation residue containing about 10,692 ppm rhodium was prepared, the distillate sample was prepared with sufficient triphenylphosphine and sufficient texanol.

A solution containing about 330 ppm rhodium and about 5 wt% triphenylphosphine (about 60 moles of free triphenylphosphine per mole of rhodium) was prepared by diluting with about 75 psi of carbon monoxide, hydrogen and Propylene was used to promote hydroformylation of propylene in an about 100 ° C. stirred autoclave reactor in a 1: 1: 1 molar ratio. In the reaction using this concentrate as the source of rhodium of the catalyst, the rhodium complex catalytic activity was about 39% compared to the new rhodium complex catalytic activity using rhodium dicarbonyl acetyl acetoneate as the source of rhodium under the same conditions.

Another sample of the diluted rhodium complex concentrate solution prepared as described above on the same day was first washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and used for hydroformylation of propylene under the same conditions as described above. Before drying. In this case, the rhodium complex catalytic activity was increased to about 68% compared to the new rhodium complex catalytic activity under the same conditions.

Example 18

400 ppm obtained from a continuous hydroformylation reaction in which propylene is reacted with carbon monoxide and hydrogen to produce butyraldehyde in the presence of a rhodium complex catalyst consisting primarily of carbon monoxide and triphenylphosphine and a rhodium complex catalyst consisting of free triphenylphosphine A 55 gallon waste hydroformylation reaction medium sample containing less than Rhodium was subjected to an LUWA 1.4 square foot thin film evaporator operating at an outer wall temperature of about 260 to 280 ° C. and 90 to 94 mmHg charge rate of 120 to 140 pounds / hour / ft ² . Concentration at to remove aldehydes and other low boiling materials. The distillation residue of the first distillation was subjected to secondary distillation in a medium stage of 280 to 300 ° C., 4 to 9 mmHg, and a charge rate of 13 to 143 pounds / hour ft ² to remove butyraldehyde diol esters and phosphine compounds. . Finally, the second distillation residue was further concentrated in an evaporator at 305 ° C., 4 mmHg and a charge rate of 7.4 to 255 pounds per hour / ft ² , containing about 947 ppm rhodium and a small amount of triphenylphosphine, the remainder being triphenyl A highly viscous rhodium complex concentrate distillation residue consisting of high boiling organic materials such as phosphine oxide and aldehyde pentapolymer is obtained.

로 희석하여 약 300ppm 로디움과 약 5중량% 트리페닐포스핀(로디움 1몰당 유리 트리페닐포스핀 약 65몰)을 함유하는 용액을 제조하고, 용액 시료는 이어 약 75psi의 일산화탄소, 수소 및 프로필렌이 1 : 1 : 1몰 비율 상태의 약 100℃ 교반 오토크래브 반응기에서 프로필렌의 하이드로포밀화를 촉진시키는 데 사용하였다. 이 농축액을 촉매의 로디움원으로 사용한 반응에서의 로디움 복합체 촉매활성은 동일 조건하에서 로디움디카보닐아세틸 아세톤에이트를 촉매의 로디움원으로 사용한 새로운 로디움 복합체 촉매활성과 비교하여 약 22%였다. 이같은 저활성도는 어느정도는, 사용한 증류온도가 높은 것과 농축물을 시험전 약 8 내지 9개월동안 거의 공기 부재상태에서 보관한데 기인한다.Samples of Rhodium Complex Concentrate Distillation Residues containing approximately 9473 ppm rhodium were loaded with sufficient triphenylphosphine and sufficient texanol.

Dilute with to prepare a solution containing about 300 ppm rhodium and about 5 wt% triphenylphosphine (about 65 moles of free triphenylphosphine per mole of rhodium), and the solution sample was then subjected to about 75 psi of carbon monoxide, hydrogen and propylene This was used to promote hydroformylation of propylene in a about 100 ° C. stirred autoclave reactor in a 1: 1: 1 molar ratio. The rhodium complex catalytic activity in the reaction using this concentrate as the rhodium source of the catalyst was about 22% under the same conditions as the new rhodium complex catalytic activity using the rhodium dicarbonylacetyl acetoneate as the source of the catalyst. This low activity is, to some extent, due to the high distillation temperatures used and the concentration of the concentrate in the absence of air for approximately 8 to 9 months prior to testing.

Another sample of the diluted rhodium complex concentrate prepared as described above was first washed with 5% by weight aqueous sodium bicarbonate solution and then washed with water and then dried before use in hydroformylation of propylene under the same conditions as described above. In this case, the rhodium complex catalytic activity was increased to about 46% compared to the new rhodium complex catalytic activity under the same conditions.

A series of other samples of the rhodium complex concentrate distillation residue containing about 9473 ppm rhodium were treated via air or nitrogen at varying times at the temperatures outlined in Table III below. A portion of each treated sample was diluted with a solution containing 300 ppm rhodium and about 5 wt% triphenylphosphine in the same manner as described above to promote the hydroformylation of propylene under some of the same conditions given above. Used to. The other part of each preparation thus prepared was first washed with 5% by weight aqueous sodium bicarbonate solution and water in the same manner as described above before being used for hydroformylation of propylene under the same conditions as described above. A comparison of the new rhodium complex catalytic activity of rhodium catalytic activity using this gas-treated concentrate as the source of rhodium for the catalyst is given in Table III below.

TABLE III

Example 19

400 ppm obtained from a continuous hydroformylation reaction in which propylene is reacted with carbon monoxide and hydrogen to produce butyraldehyde in the presence of a rhodium complex catalyst consisting mainly of carbon monoxide and triphenylphosphine and a rhodium complex catalyst consisting of free triphenylphosphine A 4997-pound waste hydroformylation reaction medium sample containing less than rhodium and whose catalytic activity drops to about 30% of the new axon activity is operated at an outer wall temperature of about 187 ° C, about 150 mmHg and a charge rate of about 416 pounds / hour. The aldehydes and other low boiling materials were removed by concentration in a Pfaudler 13.4 cubic foot thin film evaporator. The distillation residue of this primary distillation was subjected to secondary distillation in an evaporator of about 237 ° to about 66 mmHg and a charge rate of about 296 pounds per hour to remove butyraldehyde diol esters and phosphine compounds. The evaporative residue from the second distillation was collected, which contained 17.7% of the waste hydroformylated medium charge and contained 98.4% (1560 ppm rhodium) of the charge rhodium. This secondary distillate residue sample was further concentrated in an evaporator at about 272 ° C., about 3 mmHg and a charge rate of about 195 pounds / hour, resulting in 2.3% of the original waste hydroformylated media charge and 79% of the load Rhodium load (8329 ppm Lodi). To give a final viscous rhodium complex concentrate distillation residue.

로 희석하여 약 200ppm 로디움과 12중량% 트리페닐포스핀을 함유하는 용액을 제조하였다. 이어서 이와같이 제조한 각산소화 용액의 일부를 10중량% 중탄산나트륨 수용액과 물로 세척하였다. 세척전 및 세척후의 각 시료용액을 일산화탄소, 수소 및 프로필렌하에 약 105℃ 연속반응로에서 프로필렌의 하이드로포밀화를 촉진시키는 데 사용하였다.Rhodium complex concentrate distillation residue samples obtained from the second distillation (1560 ppm rhodium) and the third distillation (8329 ppm rhodium) were prepared by stirring each sample concentrate for 16 hours at room temperature under about 100 psi air pressure. Oxygenated. Each oxygenated sample concentrate as well as each oxygenated sample concentrate was filled with sufficient triphenylphosphine and sufficient texanol.

Dilution with gave a solution containing about 200 ppm rhodium and 12 wt% triphenylphosphine. Subsequently, a part of the prepared oxygenated solution was washed with 10% by weight aqueous sodium bicarbonate solution and water. Each sample solution before and after washing was used to promote hydroformylation of propylene in a continuous reactor at about 105 ° C. under carbon monoxide, hydrogen and propylene.

In addition, the same hydroformylation reaction was carried out using the original waste hydroformylation reaction medium (the original feed material used in the examples) washed with 10% by weight sodium bicarbonate and water. The catalytic activity or butyraldehyde production rate for each solution is measured as g-mol of butyraldehyde per hour per liter of solution and compared to the new rhodium complex catalytic activity under the same conditions. The results of this example are shown in Table IV below.

Table IV

Example 20

로 희석하여 약 300ppm 로디움을 함유하는 용액을 제조하고 공기존재하에서 교반시키면서 각 용액의 시료를 주기적으로 분취하고 여기에 충분한 트리페닐포스핀을 첨가하여 10중량% 트리페닐포스핀을 함유하는 하이드로포밀화 매질을 제조하였다. 이어 10중량% 중탄산나트륨 수용액과 물로 세척하기전과 세척한후의 하이드로포밀화 매질을 실시예 17에 기술한 것과 동일한 방식으로 프로필렌의 하이드로포밀화를 촉진시키는 데 사용하였다. 이 농축액을 촉매의 로디움원으로 사용한 로디움 촉매활성을 동일 조건하에서 로디움 디카보닐세틸 아세톤에이트를 촉매의 로디움원으로 사용한 새로운 로디움 복합체 촉매와 비교하였으며 이 실시예 결과를 다음 표 Ⅴ에 나타내었다.Samples of rhodium complex concentrate distillation residue obtained from the second distillation (1560 ppm rhodium) and the third distillation (8329 ppm rhodium) of Example 19 were each filled with sufficient texanol.

Dilution with water to prepare a solution containing about 300 ppm rhodium, and a sample of each solution was periodically collected while stirring in the presence of air, and sufficient triphenylphosphine was added to it to form a hydrophobic solution containing 10 wt% triphenylphosphine. Mildening media were prepared. A hydroformylation medium before and after washing with 10 wt% aqueous sodium bicarbonate solution and water was then used to promote hydroformylation of propylene in the same manner as described in Example 17. The rhodium catalytic activity using this concentrate as the source of rhodium for the catalyst was compared with the new rhodium complex catalyst using rhodium dicarbonylcetyl acetoneate as the source of rhodium under the same conditions and the results of this Example are shown in Table V below. .

TABLE V

Example 21

로서 희석하고 1.31g의 테트라부틸하이드로퍼옥사이드와 95℃에서 4시간 동안 혼합하였다. 이어 이같이 제조한 31.8g의 용액시료를 3.8 트리페닐포스핀 및 2.5g 추가 텍사놀

과 혼합하고, 추가로 1시간 95℃에서 교반하였다. 이 최종 용액을 10중량% 중탄산나트륨 수용액 동용적으로2회, 이어서 35ml 물로 세척하였다. 이 세척 처리후에 수득한 용액은 252ppm 로디움 및 9중량% 트리페닐포스핀을 함유하는 데, 실시예 17에서 기술한 것과 동일 방식에 따라 프로필렌의 하이드로포밀화에 사용하였다. 이 로디움 농축물을 촉매의 로디움원으로 사용하는 로디움 촉매활성은 로디움 디카보닐 아세틸 아세톤에이트를 동일 조건하에서 촉매의 로디움원으로서 사용하는 새로운 로디움 복합체 촉매활성과 비교하여 약 83%였다.2.11 g of rhodium complex concentrate distillation residue sample containing about 14,200 ppm rhodium prepared as described in Example 18 was subjected to 102 ml texanol.

It was diluted as and mixed with 1.31 g of tetrabutylhydroperoxide at 95 ° C. for 4 hours. 31.8 g of the sample prepared in this way was then added with 3.8 triphenylphosphine and 2.5 g of additional texanol.

It was mixed with and stirred at 95 ° C for further 1 hour. This final solution was washed twice with 10% by weight aqueous sodium bicarbonate solution followed by 35 ml water. The solution obtained after this wash treatment contained 252 ppm rhodium and 9 wt% triphenylphosphine, which was used for hydroformylation of propylene in the same manner as described in Example 17. The rhodium catalytic activity using this rhodium concentrate as the rhodium source of the catalyst was about 83% compared to the new rhodium complex catalytic activity using rhodium dicarbonyl acetyl acetoneate as the source of the catalyst under the same conditions.

Example 22

An oil heating type glass falling film evaporator was used (evaporation area 814 cm ² , 3 tubes, length 600 mm, internal diameter 14.4 mm). Propylene hydroformylation reaction containing about 0.124 g rhodium (220 ppm rhodium) as a hydrocarbonyl triphenylphosphine rhodium catalyst, which was heated to 210 ° with a heating medium and used slightly deactivated. The product was heated to hot oil and 203 ° C. and then charged to a falling film evaporator at a pressure of 1.009 millibars and a charging rate of 563 g / hour. The top product is a low boiling point material of 84.4 g / hour (corresponding to 15% by weight) consisting mainly of butyraldehyde which is almost free of rhodium (less than 0.1 ppm rhodium by weight). The bottom product is a high boiling point product of 478.6 g / hour.

This high boiling point product is directly charged into a glass thin film evaporator (evaporation area 900 cm ² , rotation speed 900 rpm) heated to 212 ° C. with hot oil and operated at 4 millibar pressure without cooling. Distillate containing no rhodium at 469.5 g / hr rate is obtained as a top product (rhodium content is not measurable, less than 0.1 ppm). The distillate from the thin film evaporator is rectified in a rectifier system in which each tower consists of two continuous operation towers with 20 trays. The liquid product is charged to the tenth tray of the first column and the bottom product of the first column, which is also liquid, Is loaded into the 10th tray of the second tower. The first tower is operated at 40 millibars of tower static pressure and 30 millibars of differential pressure. The column top temperature is 180 ° C., and the reflux ratio is 1. Under this condition, the distillate contains 0.12% by weight of triphenylphosphine. The second column is operated with a column top pressure of 30 millibars, a tower top temperature of 236 ° C, a tower bottom temperature of 280 ° C and a reflux ratio of 0.4. The recovered triphenylphosphine is 90% concentration by gas chromatograph analysis. This product, when used for the manufacture of rhodium catalyst, is equivalent to fresh triphenylphosphine at equivalent triphenylphosphine content and no further purification is required. The second bottom product contains triphenyl phosphine oxide. High viscosity solution is obtained at the bottom of the thin film evaporator at a rate of 9.1 g / hour (corresponding to 1.62% by weight relative to the falling film evaporator charge). This solution contains total rhodium (13,800 weight ppm rhodium) and 3.5 weight percent phosphorus. Triphenylphosphine (TPP) was added to this solution at 30 g / hour and diluted with 530 g / hour of n-butanol to prepare a 220 ppm rhodium solution having a phosphine / rhodium molar ratio of 102.

Thus the hydroformylation catalyst solution using a laboratory device which is continuously movable in the synthesis gas of 133Nl / hour propylene of 125g / hour at 100 ℃ and 17 bar 2kg (1 CO:: H _2: 1). This catalyst solution has greater activity than the catalyst used in the falling film evaporator in this example. In other words, the normal / iso ratio is about 1.65.

If 9.1 g / hour of material stream 1b is changed to 33.3 g / hour of 90% triphenylphosphine, the second column distillate, instead of 30 g / hour of pure triphenylphosphine, which is converted into 527 g / hour of n-butanol. When diluted and hydroformylated according to this example data, 2 kg of this mixture is usually obtained with the same results within the laboratory and analytical range.

Unexperimental results can be obtained when the thin film evaporator is operated according to the data of this example with a temperature of 250 ° C. and a load of 1150 g / hour.

Example 23

Based on the data of Example 22, the reaction product of 1486 g / hour was concentrated in an oil heated glassy falling film evaporator. The concentrated product was charged to a glassy thin film evaporator at 263 g / hr rate without precooling as described in Example 1. This distilled at a rate of 1122 g / hour, leaving a residue of 141 g / hour (corresponding to 9.5% by weight of the falling film evaporator charge), which contained 2.0% by weight of phosphorus as well as a converter (2.315 ppm by weight). It is contained. 61 g / hour triphenylphosphine was added to the solution and diluted with 1280 g / hour n-butanol to prepare a 22 ppm rhodium solution with a phosphine / rhodium molar ratio of 102.

In this embodiment the catalyst solution using the apparatus described in 22 134.8g / propylene of time temperature and pressure 17 100 ℃ 2kg pressure synthesis gas of 144Nl / hour (CO: H ₂ is from 1: 1) and the hydroformylation It was used to make. The dicatalyst solution has greater activity than the catalyst used in the falling film evaporator of this example.

Comparative experimental results can be obtained when the thin film evaporator is operated at a temperature of 198 ° C. and a load of 620 g / hour according to the data of this example.

Comparative Example 24

The same raw material was concentrated to 85% in the glass falling film evaporator described in Example 22. This concentrate was further concentrated at 1044 g / hour using a thin film evaporator with a pressure of 3 millibars and a heating medium temperature of 147 ° C. as described in Example 22. It was evaporated at a rate of 430 g / hour, which contained no rhodium. There was also 614 g / hour residue remaining with a 50% concentration in relation to the material stream recycled to the falling film evaporator. This residue contained the total amount of rhodium and the concentration of rhodium was 440 ppm by weight. The residue also contains 1.4% phosphorus compound in terms of phosphorus. To this solution was added 614 g / hour n-butanol to prepare a 220 weight ppm rhodium solution with a phosphine / rhodium molar ratio of 106.

2 kg of this catalyst solution was used to hydroformylate with 145 Nl / hour syngas (CO: H ² is 1: 1) at 100 ° C. and pressure 17 bar using the apparatus described in Example 22. This catalyst solution has greater activity than the catalyst used in the falling film evaporator of this example.

Examples 22 to 24 describe one aspect of the present invention further described below.

The process of the present invention has the advantage of recovering a highly selective catalyst containing active rhodium and phosphine in a simple and economical way. Compared with conventional processes or regeneration of scraped or partially deactivated rhodium catalysts, the process of the present invention has another advantage that no chemicals are used to recover catalysts containing active rhodium and phosphine. According to the process of the invention it is possible to recover the phosphine as well as the active rhodium catalyst. According to the present invention, catalysts containing active rhodium and phosphine can be recovered in a simple and economical manner, so if the activity loss of the catalyst is relatively small, the rhodium catalyst can be regenerated to obtain hydroformylation at a higher time yield or more. Can proceed with great selectivity. It is surprising that two recovery rhodium catalysts have not only high activity but also high selectivity.

Contrary to what is known in many reports of the inventive process using gentle distillation into at least two material streams, the rhodium compound is in the form of a compound that is not decomposed or deactivated and is not soluble in the metal but is soluble in solution. It is particularly surprising that their presence increases their activity and selectivity. More intense concentrations only increase the viscosity of the rhodium compound solution.

The improvement in activity and selectivity of the recycled rhodium catalyst is surprising. From the reaction product of the rhodium catalyzed oxosynthesis, the liquid reaction product containing the partially deactivated spent catalyst was distilled under mild conditions to reactivate and recover the heavily deactivated spent rhodium and phosphine-containing catalyst. Distillates containing almost no rhodium and small amounts of distillation residues containing virtually all rhodium are obtained. This distillation residue can be reused as a hydroformylation catalyst after adding an appropriate amount of phosphine, fresh or regenerated thereto, and diluting with the aldehyde to be produced. Surprisingly, this recovery catalyst has improved activity and selectivity.

Almost no rhodium-containing distillate (mass stream 1a) is the value of the resulting aldehydes, intermediate streams containing species, phosphine fractionation and phosphine oxide forms suitable for activating new or recovered rhodium catalysts. It is separated into a rectified residue stream that contains little phosphine. The distillation of this distillate (mass stream 1a) may consist of steps.

The distillation separation of at least two material streams involves heating the reaction mixture at 150 to 300 ° C., preferably at 170 to 270 ° C., in particular at 200 to 220 ° C. and preferably in two steps. The use of reduced pressure has the same effect as the use of an inert carrier gas stream. In this regard, the heating should be carried out gradually for the purpose of preventing overheating. Distillation at each distillation stage can be carried out using a heating system, but be careful of overheating. Distillation should be performed within a short time using a thin film evaporator or falling film evaporator.

By distillation, the waste rhodium and phosphine-containing mixture is concentrated to 0.1-30% by weight, preferably 1-10% by weight, in particular 1.5-5% by weight distillation residue (mass stream 1b). The distillation of the reaction mixture containing the partially deactivated rhodium catalyst into at least two material streams is carried out in one or more distillation stages, e.g., the first distillation stage comprises 50 to 500 ppm by weight of the bottoms product. Concentration, and in the second distillation step, it can be concentrated to 1000 to 25,000 ppm rhodium. Wherein the second distillation step is operated under reduced pressure.

Distillation to the stream can proceed discontinuously or continuously. If two or more distillation stages are used, the second stage distillation preferably proceeds continuously under reduced pressure. Likewise, the discharge of partially activated spent rhodium catalyst from the hydroformylation reactor may be continuous or discontinuous. In the discontinuous discharge method of the deactivation catalyst, the contents before the reactor are discharged, in the continuous method only a part of the reactor contents is discharged, and the recovered reactivation catalyst is continuously recycled to the reactor.

If the recovered rhodium concentrate (mass stream 1b) is reused, in some cases an amount of phosphine should be added to ensure that at least 100 g morphophosphine per 1 g atom of rhodium is present in the reaction medium. If the material stream 1b contains more than 100 g moles of phosphine per 1 g atom of rhodium, no phosphine addition is required. New or regenerated phosphines can be used for catalyst preparation, but the use of regenerated phosphines is recommended. It is not necessary to use this regenerated phosphine in a pure state, and it can also be used as a mixture containing other compounds which do not adversely affect catalytic activity or selectivity. Examples of suitable phosphines include triphenylphosphine, in particular triphenylphosphine.

This process of activation activation and catalyst recovery is suitable for hydroformylation of olefins, in particular C ₂ to C ₄ olefins, in particular for propylene to hydroformylation with butanal.

The process of the present invention improves the recovery of the active rhodium phosphine-containing catalyst and significantly simplifies its preparation. According to the present invention, there is no problem regarding environmental pollution since there is no exhaust gas or other emissions.

Those skilled in the art will recognize that various modifications and changes can be made to the present invention, and that such modifications and changes are included in the scope and concept of the present specification and appended claims.

Claims (1)

Aldehydes are prepared by hydroformylating olefins with hydrogen and carbon monoxide in the presence of a hydroformylation reaction medium consisting of a soluble rhodium complex catalyst and at least 10 moles of free triarylphosphine per mole of rhodium having catalytic activity in the medium. In a hydroformylation process, a waste hydroformylation reaction medium containing partially deactivated rhodium complex catalyst and free triarylphosphine is subjected to a temperature of about 20 to about 350 ° C. and about 1,000 mmHg to 1 × 10 ^−6. Distilled under pressure of mmHg, one stream is the distillation residue of the rhodium complex concentrate containing most of this catalytic rhodium and concentrated to about 0.1 to about 30% by weight of the spent hydroformylation reaction medium and the remainder of the material stream. (S) comprises at least two separations consisting mainly of one or more volatile distillates of the spent hydroformylation reaction medium. Rhodium complex concentrate prepared by concentrating the prepared material stream as a catalyst for the rhodium source.