CS248736B2 - Production method of aldehydes - Google Patents

Abstract

In the prodn. of aldehydes by reacting olefins with CO and H2 in the liquid phase in the presence of water and water-soluble Rh-phosphine complex cpds. (I) at 20-150 deg.C and 1-200 bar (100- 20 x 10 power 3 kPa), (I) contg. trisulphonated or tricarboxylated triarylphosphones (II) are used as catalyst and the reaction medium contains a solvent promoter (III). Pref. (II) is of the formula P(Ar1(X1M)(Y1n1))(Ar2(X2M)(Y2n2)) (Ar3(X3M)(Y3n3))(IIA): Ar1, Ar2 and Ar3 = phenyl or naphthyl gps.; esp. phenyl; Y1, Y2 and Y3 = linear or branched 1-4C alkyl, alkoxy, halogen, OH, CN, NO2 or R1R2N- gps.; R1 and R2 = linear or branched 1-4C alkyl; X1, X2 and X3 = a carboxylate (COO-) and/or sulphonate (SO3-) gp.; esp. a sulphonate gp.; n1, n2 and n3 independently = 0-5; M = an alkali alkaline metal, Zn, NH4 or quat. ammonium of the formula N(R3R4R5R6)+; R3, R4, R5 and R6 = linear or branched 1-4C alkyl.

Description

The invention,. concerns - the way. of the production of aldehydes by hydroformylapping according tofinins. . presence in water-soluble rhodium complex compounds as catalysts.

It is known to produce aldehydes and alcohols by reacting olefins with carbon dioxide and hydrogen. The reaction is catalysed by metal hydridocarbonyls, especially Group 8 metals of the Periodic System. Next to cobalt, which is like catalysts _with heat. used in a large .rozsa.hu, .. acquires - at ... the last. ' time - increasing importance of rhodium. As opposed to · ke - cobalt, it "allows. ... rhodium carry out - - reaction. at low pressure. In addition, straight-chain n-aldehydes are formed, in particular, and only to a minor extent iso-aldehydes. Finally, the hydrogenation of olefins to saturated hydrocarbons with rhodium catalysts is considerably lower than with cobalt catalysts.

In the methods established in the art, the rhodium catalyst is used in the form of modified metal hydridocarbonyl, which additionally contain any excess ligands. Tertiary phosphines or phosphites have proven particularly useful as ligands. Their use allows to reduce the reaction pressure to below 30.1 ³ kPa.

In this process, however, the problems of separating the reaction products and recovering the catalysts in the reaction product are homogeneously dissolved, usually for this purpose. the reaction product of the reaction mixture distills off. However, this process can be carried out in hydroformylation due to the thermic sensitivity of the resulting aldehydes and alcohols. - lower olefins; that is, about olefins; The β-5-carbon atoms in the molecule. In addition, it has been shown that the thermic load of the distillation of the substance also leads to appreciable losses. of the catalyst by decomposition of the rhodium compound.

The deficiencies described are eliminated by the use of catalyst systems which are soluble in water. Such solubilizers are described, for example, in German Patent Specification No. 26 27 354. The solubility of rhodium complex compounds is achieved by the use of sulfonated triarylphosphines as part of the complex. The separation of the catalyst from the reaction product after completion of the hydroformylation reaction in this process variant is effected simply by separation of the aqueous and organic phases, i.e. without distillation and thus without additional thermal processes. In addition to the sulfonated triarylphosphines, carboxylated triarylphosphines are also used as part of the water-soluble complex rhodium complex compounds.

The known methods have proven to work well for the hydroformylation of low olefins. especially ethylene and propylene. When higher olefins such as hexene, octene or decene are used, the conversion decreases noticeably, so that the economic efficiency of the reaction is no longer given on a technical scale.

The decrease in conversion is due to the reduced solubility of the higher olefins in water, since the reaction between the reactants takes place in the aqueous phase.

It is, however, known from DOS 31 31 127 to carry out hydroformylation of olefinic compounds using aqueous and non-miscible, or only slightly miscible organic phases in the presence of a dissolution mediator.

The practice of this reaction is exclusively limited to the use of monosulfonated or monocarboxylated triarylphosphines as part of the rhodium complex compound. In particular, it appears that the monosulfonated triphenylphosphine achieves only a short lifetime and is therefore not suitable for repeated use.

It is therefore a task to overcome the previously described disadvantage and to develop a process which allows the hydroformylation of even higher olefins in a multiphase system consisting of an aqueous catalyst solution and organic starting materials and optionally reaction products as well as gaseous reactants.

According to the invention, the above object is achieved by a process for the production of aldehydes of carbon monoxide and hydrogen in the liquid phase in the presence of water and water-soluble complex rhodiophosphine compounds at temperatures of 20 to 150 ° C and pressures of 0.1 to 20.10 ³ kPa. Rhodium complex compounds containing trisulfonated or tricarboxylated triarylphosphines are used as catalysts and the reaction medium comprises a solubilizer.

Surprisingly, in the presence of trisulfonated or tricarboxylated triarylphosphines as part of rhodium complex compounds and in the presence of a dissolution mediator, olefin hydroformylation is surprisingly successful with sustained high conversion and high selectivity, without producing waste due to the rapid decomposition of the catalyst.

The rhodium compounds used in the catalyst of the present invention contain trisulfonated or tricarboxylated triarylphosphines of the general formula in complex bond

where

Ar ¹ , Ar ² and Ar ³ represent a phenyl or naphthyl group,

Y ¹ , Y ² , Y ³ represent a straight or branched chain alkyl group having 1 to 4 carbon atoms, a straight or branched chain alkoxy group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, a cyano group, a NO 2 group, or R ¹ R ² N, wherein R ¹ and R ² represent a straight or branched alkyl group having 1 to 4 carbon atoms,

X ¹ , X ² , X ³ denote a carboxylate (COO ^- ) and / or sulfonate (SO 3 ^- ) residue, n 1, P 2,, m are the same or different integers 0 to 5,

M is an alkali metal ion, an equivalent of an alkaline earth metal or zinc ion, an ammonium ion or a quaternary ammonium ion of the formula

N (R ³ R ⁴ R ⁵ R ⁶ ) ⁺ , where

R ³ , R ⁴ , R ⁵ , R ⁶ represent a straight or branched chain alkyl group having 1 to 4 carbon atoms.

According to one preferred embodiment, to24873G

In this process, the radium compounds comprise complexing compounds of the above formula wherein Ar ¹ , Ar ² , Ar ^{3 are} phenyl and X ¹ , X ² , X ^{5 are} sulfonate.

Dissolution mediated is understood to mean substances or mixtures of substances which are compatible with both the aqueous and the organic phases, and in particular are soluble at elevated temperatures in both phases. Such agents are known and are referred to as phase transition agents, surfactants, or amphiphilic reagents or surfactants.

their effect lies in particular. by altering the physical properties of the interface between the two liquid phases and thereby facilitating the transition of the organic renctant into the aqueous catalyst phase. In this context, it is of particular importance that the mediated dissolution has no negative effect on the activity of the catalytically active metal. Depending on the chemical composition, mediated dissolution is distinguished into anionic, cationic and non-ionic.

Examples of anionic solubilizers that may be used in the process of the invention are salts of C8-C20 carboxylic acids, especially saturated C12-C18 fatty acids, such as lauric acid, myristic acid and stearic acid. Anionic dissolution agents further include alkyl sulfonates and alkylarylsulfonates such as alkylbenzenesulfonates and alkylnaphthalenesulfonates.

Neutral or non-ionic solubilizers include, in particular, ethylene oxide adducts such as alkylpolyethylene glycols (obtained by adding higher molecular alcohols to ethylene oxide), alkylphenylpolyethylene glycols (obtained by adding phenols to ethylene oxide) and acylpolyethylene glycols (obtained by adding fatty acids to ethylene oxide).

Particularly suitable cationic solubilizers are quaternary onium compounds, especially ammonium salts. In particular, the compounds of the general formula have proven useful

wherein a branched chain of 6 to 25 carbon atoms, an aryl radical of 6 to 25 carbon atoms which is optionally substituted, or a radical of formula

R ⁷ —CONH — СНз — CH? —CH? In which

R ⁷ represents a straight or branched chain alkyl radical of 5 to 11 carbon atoms,

В, C and D, which are the same or different, are straight or branched chain alkyl having 1 to 4 carbon atoms or ω-hydroxyalkyl straight or branched chain having 1 to 4 carbon atoms or C and D together with an atom nitrogen forms a 5- or 6-membered heterocyclic ring,

E ~ represents chloride, bromide, iodide and especially sulfate, tetrafluoroborate, acetate, methosulfate, benzenesulfonate, alkylbenzenesulfonate, toluenesulfonate, lactate or citrate.

Due to their low corrosion behavior, sulfonates, methosulfonates and lactates are suitable as anions. Examples of suitable cations which correspond to the above formula are stearyltrimethylammonium, phenyltrimethylammonium, trimethyl-1-phenylammonium, benzyltrimethylammonium, cetyltrimethylammonium, myristyltrimethylammonium, dodecylpyridinium, stearylamidomethylpyridinium, lauryltrimethylammonium, trisyltrimethylammonium, ammonium, , dodecyl-tris-4-hydroxyethylammonium or N- (β-trimethylammoniumpropyl) -n-nonanoic acid amide methosulfate.

The concentration of the solubilizer in the aqueous catalyst solution is 0.5 to 10% by weight, based on the catalyst solution.

The reaction of the olefins with hydrogen and carbon monoxide is carried out at temperatures of 20 to 150 degrees C, in particular 50 to 120 ° C, and pressures of 0.1 to 20. Výhodně ³ preferably 1. 10 ³ to 10.10 ³ kPa.

The catalyst may be added to the reaction system preformed. However, it can also be produced equally well from components, rhodium or a rhodium compound and an aqueous solution of sulfonated or carboxylated triarylphosphine, under reaction conditions in the reaction mixture, i.e. in the presence of olefins. In addition to the metallic rhodium in finely divided form, rhodium salts such as chloride, sulfate, acetate or compounds soluble in organic copper, such as rhodium-2-ethylhexanoate, or insoluble compounds such as rhodium oxides can be used as the rhodium sources.

Concentration of rhodium in aqueous solution

A represents a straight or branched chain alkyl group of 6 to 25 carbon atoms, a ω-hydroxyalkyl straight or branched chain group of 6 to 25 carbon atoms, an alkoxy radical of straight or branched chain catalyst of 10 to 2000 wt. solution. The sulfonated or carboxylated phosphine is added in an amount such that 1 to 100 mol, in particular 2 to 300 mol, of the phosphine compound per 1 gram of rhodium.

The pH of the aqueous catalyst solution should not be below 2. Generally, the pH is adjusted to 2 to 13, in particular 4 to 10.

The composition of the synthesis gas, i.e. the ratio of carbon monoxide to hydrogen, can vary within wide limits. Generally, a synthesis gas is used in which the volume ratio of carbon monoxide to hydrogen is 1: 1 or deviates slightly from this value.

The reaction can be carried out both batchwise and continuously.

The process according to the invention is successfully used in the hydroformylation of straight-chain or branched olefins having 4 or more, in particular 6, carbon atoms. The double bond in these olefins may be at the end or within the chain.

The following examples illustrate the invention in greater detail without restricting it to the embodiments described. In addition to the ratio of n-aldehyde to iso-aldehyde, the term "activity" defined as mol of aldehyde g is used to characterize the performance of the catalyst system. min and "productivity" defined as g of aldehyde cm ³ of catalyst solution. h

The formation of alcohols and hydrocarbons is minimal. Example 1 is a comparative experiment that was carried out without the addition of a dissolution mediator.

Example 1 (comparative example)

(a) Pre-catalyst production

345 ml of an aqueous solution of trisodium tri (m-sulfophenyl) phosphine containing 20.4% by weight of salt as well as 400 ppm of Rh as Rh-acetate are introduced into a 1 liter immersion throat. The synthesis gas (CO / H 2 volume ratio 1: 1) is - compressed to a pressure of 2.5 x ^{10 3} kPa. Thereafter, the reaction solution is treated with syngas for 3 hours with stirring at 125 ° C to form an active catalyst. After cooling to about 30 [deg.] C., the stirring is stopped and after a 15-minute offset, the excess solution (~ 10 g) is extruded through a dip neck and analyzed. The remainder of the solution remains in the autoclave.

b) Hydroformylation

170 g of n-hexene-1 are pumped into the solution prepared according to a) with stirring. At a constant pressure of 2.5 bar, the mixture is heated to 125 ° C and left at this temperature for 3 h. It is then cooled to 30 ° C and allowed to settle. The protruding orgnic phase is forced out by the immersion throat; Weigh (see Table 1) and test by gas chromatography.

Sub-process b) is repeated a total of three times, producing essentially the same results. The values reported for activity and productivity in Table 1 refer to the amount of aqueous and organic phases present in the autoclave. The specific gravity of the aqueous phase is 1.1304 g / cm ³ .

l

Number of hydroformylations

Conversion (% by GC)

The n / iso ratio

Organic phase (g)

Reactor aqueous phase (g) Activity

Г mol of C7 aldehyde 1 g Rh atom. min J

Productivity

J g of C7 aldehydes _______ [cm ³ of cat

1 2 3 4 0 22nd 18 18 16 18 98/2 98/2 98/2 98/2 98/2 153 167 172 175 167 346 344 343 342 344 .1,22 1.09 1.13 1,02 1.11 0,037 0,033 0,034 0,031 0,033

Example 2

Example 1 is repeated except that, according to the invention, 9.75 g of tetradecyltrimethylammonium methosulfate (2.5% by weight) is additionally added to the aqueous catalyst solution.

The specific gravity of the catalyst solution is

1.171 g / cm ³ .

Table 3

3

5. 0

Conversion (% by GC)

N / iso ratio Organic phase (g)

Reactor aqueous phase (g) Activity

C7 aldehydes 1 g Rh atom. min J

Productivity

Г aldj ^ yd ___ Ί [cm ³ cat. H solution]

Example 2 shows that activity and productivity are greatly improved by the addition of a solubilizer, without significantly impairing selectivity.

To balance the phosphorus and rhodium yields, the organic products of Example 2 were combined and analyzed after concentration. The organic product contains 0.3 ppm rhodium and 4 ppm phosphorus.

41 47 Íd8 35 42 43 95/5 96/4 96/4 96/4 96/4 96/4 168 175 185 220 176 185 374 352 341 336 306 342 2.31 2.93 3.23 2.87 3,0.21 ' '2.87 0,07.2 0.091 0,102 0,089 0,094 0,090

The following examples 3 to 9 illustrate the effect of various dissolution mediators. The results of five hydroformylations with the same catalyst solution are always summarized as the average values in Table 3. The test conditions are the same as in Examples 1 and 2.

Table 3

Example No. 1Š456789 or allowance (see below)

Quantity (%) - 1 1 1 2.5 2.5 2.5 2.5

Conversion ( ⁱ⁰ / o by GC) Activity of 1'mol of C7 aldehydes 1 18 23 1.07 1.43 [g atom Rh. min 1 Productivity g C7 aldehydes 1 cm ³ cat. h] 0.032 0.045

27 30 30 3533

1.58 1.74 1.88 2.28 2.412.36

0.049 0.054 0.056 0.069 0.0720.071

In the following examples, the concentration of the water-soluble, trisulfonated phosphine is reduced such that the sodium salt of tri (m-sulfophenyl) phosphine is 12.2% by weight.

Otherwise, the procedure is as in Examples 1 through

2. The average values of five hydroformylations with the same catalyst solution are again reported. The results are shown in Table 4.

Table 4

Example / allowance no. 10 11 12 a) 13 14 15 Dec 16 17 Concentration (%) without 5 2.5 0.5 2.5 2.5 2.5 2.5 Conversion (° / o by GC) 36 43 86 43 43.5 39 42 50 Activity 1.94 3.40 6.1 2.7 2.8 2.47 3.3 3.8 1 mole of C7 aldehydes 1 1 g atom Rh. min 1 Productivity 0,065 0,098 0.200 0,087 0,088 0,072 0,097 0,112

Fg C7 aldehydes ______ 1

Hem ^{3 of} solution cat. h J

3. Olyalcohol (HD-Ocenol 150/170 manufacturer: I-Ienkel KG)

4. Lauryltrimethylammonium chloride

5. Laurylpyridinium chloride

6. Benzyltrimethylammonium sulfate

7. Dodecyltrimethylammonium methosulfonate

8. Benzyltrimethylammonium lactate

9. Dimethylethylhexadecylammoniumbenzenesulfonate

12. Trimethyl-hexadecylammonium bromide

13. Trimethyl-hexadecylammonium bromide

14. Triethylene glycol

15. Sodium oleic acid salts

16. Sulfolane

17. Tributylhexadecylammonium lactate

Comparison of Tables 3 and 4 shows the effect of the ratio of phosphorus and rhodium on the amount of conversion during hydroformylation. Clearly, the baseline activity level (= about 2) at a lower Rh / P ratio of about 1: 50 (Table 4) is about twice as high as at 1: 100 (Table 3} (= 1). The conversion rate at the lower P / Rh ratio obtainable by the addition of the dissolution mediator according to the invention still exceeds.

To balance the phosphorus and rhodium yields, the organic products of Example 12 were combined and analyzed after concentration. The organic product contains 0.41 ppm rhodium and 6.63 ppm phosphorus.

Claims (4)

A process for producing aldehydes by reacting olefin with carbon monoxide and hydrogen in the liquid phase in the presence of water and water-soluble rhodium-phosphine complex compounds at a temperature between 20 and 150 ° C and a pressure of 0.1: 1. 103 _and 20103 kPa, characterized in that the reaction is carried out in a reaction medium containing solubilizers and a catalyst formed · rhodium complex compounds containing or trisulphonated trikarboxylované triarylphosphines of the formula wherein Ar 1, Ar ² and Ar 3 represent a phenyl or naphthyl group, Y 1, Y 2 and Y 3 represent a straight or branched alkyl group having 1 to 4 carbon atoms, a straight or branched alkoxy group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, a cyano group, a nitro group or a group NRXR2 , in which R 1 and R 2 represent a straight or branched chain alkyl group having 1 to 4 carbon atoms, X1, X2 and ^X3 are a carboxylate radical of the formula COO and / or sulphate 'residue of formula SO ~, ni, n2 and n3 prominent in the same or different numbers from 0 to 5 and M represents an alkali metal ion, an equivalent of an alkaline earth metal or zinc ion, an ammonium ion or a quaternary ammonium ion of the formula N (R 3 R 1 R 5 R 6) +, wherein R ^3, R 1, R and ^R represent an alkyl group with straight or branched chain containing one to four carbon atoms. 2. Method according to claim 1, characterized in that a catalyst is used having the above general formula wherein Ar1, Ar2 and Ar3 represent a phenyl radical and X 1, X 2 and X ³ represent a sulfate radical, the other symbols have the meanings given in point 1 . 3. A process according to claims 1 and 2, characterized in that the compound of the general formula is used as the solubilizer r. ' where A is a straight or branched chain alkyl group having 6 to 25 carbon atoms, a ω-hydroxyalkyl straight or branched chain having 6 to 25 carbon atoms, a straight or branched chain alkoxy group having 6 to 25 carbon atoms, C 6 -C 25 optionally substituted or a radical of formula R ⁷ -CONH-CH 2 CH 2 CH 2 in which R ⁷ represents a straight or branched chain alkyl radical of 5 to 11 carbon atoms, B, C and D, which are the same or different, represent a straight or branched chain alkyl group having 1 to 4 carbon atoms or a straight or branched chain alkyl group having 1 to 4 carbon atoms, or C and D together with an atom nitrogen forms a 5- or 6-membered heterocyclic ring, E - represents chloride, bromide, iodide and especially sulfate, tetrafluoroborate, acetate, methosulfate, benzenesulfonate, alkylbenzenesulfonate, toluenesulfonate, lactate or citrate. 4. The process according to claim 1, wherein the concentration of the solubilizer in the aqueous catalyst solution is from 0.5 to 10% by weight, based on the catalyst solution.