CA2258280A1 - Catalyst and a process for preparation of aldehydes in the presence of said catalyst - Google Patents
Catalyst and a process for preparation of aldehydes in the presence of said catalyst Download PDFInfo
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- CA2258280A1 CA2258280A1 CA002258280A CA2258280A CA2258280A1 CA 2258280 A1 CA2258280 A1 CA 2258280A1 CA 002258280 A CA002258280 A CA 002258280A CA 2258280 A CA2258280 A CA 2258280A CA 2258280 A1 CA2258280 A1 CA 2258280A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
- B01J31/4046—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals containing rhodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
- B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a catalyst containing rhodium and a compound of the general formula (I), in which R1, R2 and R3 are identical or different and independently of each other are hydrogen, an alkyl group or alkoxy group with 1 to 4 carbon atoms, an alkenyl group with 2 to 4 carbon atoms, or R1 and R2 including the carbon atoms connected therewith in each case form a ring with 6 carbon atoms, m and n independently of each other are 0 or 1, and (m+n) is equal to 1 or 2, and R is an unsubstituted phenyl radical or naphthyl radical or a phenyl radical or naphthyl radical substituted by an alkyl group with 1 to 4 carbon atoms, an amino group or dialkyl amino group with a total of 2 to 8 carbon atoms. The invention also relates to a process for preparation of aldehydes by reaction of an olefinic compound having 2 to 20 carbon atoms with carbon monoxide and hydrogen in the presence of said catalyst.
Description
CA 022~8280 1998-12-23 r~ L ~ r i ~ S A~ ' ?' ~
WO 97/49490 T F' '~ L~ 0.~ PCT/EP97/03169 Description Catalyst and a process for the preparation of aldehydes in the presence of this catalyst The present invention relates to a novel catalyst and a process for - - preparing aldehydes by reacting olefinic compounds with carbon monoxide and hydrogen in the presence of this catalyst.
Owing to their chemical properties, aldehydes are an important group oforganic compounds. They can, for example by means of an aldol reaction with themselves or with another C-H-acid compound (methylene component), be converted into the corresponding aldols or, after 15 dehydration of the aldol, into the corresponding unsaturated condensation products. Aldehydes can also be oxidized to give the corresponding carboxylic acids or reduced to give the corresponding alcohols. Reaction of aldehydes with ammonia or amines gives imines or Schiff bases which can be reacted with hydrogen to form the corresponding amines.
Aldehydes are obtained on an industrial scale by hydroformylation of olefinic compounds. The reaction of the carbon-carbon double bonds with carbon monoxide and hydrogen results in the formation of, as shown schematically in the following reaction equation for a terminal olefin, mixtures of straight-chain and branched aldehydes.
R CH=CH2 ~ R CH CH3 + R CH2 CH2 CHO
CHO
Depending on the reaction conditions, mixtures having different compositions are obtained. In many cases, mixtures having as high as possible a proportion of straight-chain aldehydes and as low as possible a proportion of branched aldehydes are desired. Apart from the reaction CA 022~8280 1998-12-23 conditions such as pressure and temperature, the hydroformylation catalyst used exercises a decisive influence on the course of the reaction and the composition of the reaction mixture.
5 In the hydroformylation of olefins, hydroformylation catalysts which have been found to be particularly useful are rhodium catalysts containing phosphorus-containing ligands. Suitable phosphorus-containing ligands are phosphines cr phosphi'es. DE-C 17 93 069 describes such a hydro-formylation process.
However, a disadvantage is that the phosphites and in particular the phosphines are not stable toward oxygen and sulfur and are oxidized even by very small amounts of oxygen and/or sulfur, giving phosphates, thiophosphates, phosphine oxides and/or phosphine sulfides.
15 The oxygen gets into the reaction mainly via the olefin used as starting material, while the sulfur is introduced into the reaction in the form of sulfur-containing compounds, for example as H2S, via the synthesis gas.
Oxygen and/or sulfur have an adverse effect even in very small amounts 20 since after the hydroformylation is complete the catalyst is usually separated from the reaction product, for example by distillation, and reused in the hydroformylation stage. There it again comes into contact with the oxygen originating from the starting olefin and the sulfur or the sulfur-containing compound introduced with the synthesis gas. As a result, further 25 amounts of phosphite or phosphine are reacted with oxygen and/or sulfur.
The resulting phosphinic acids, thiophosphates, phosphine oxides and phosphine sulfides no longer function as complexing ligands and are thus no longer catalytically active. In addition, sulfur-containing compounds frequently have an adverse effect on catalytic processes and act as 30 catalyst poisons.
The phosphates, thiophosphates, phosphine oxides and phosphine sulfides formed are undesired in the hydroformylation and therefore have to be removed. Their removal proves, like the work-up of the catalyst, more precisely rhodium, to be difficult and is technically complicated.
CA 022~8280 1998-12-23 Although the phosphites are somewhat less sensitive to oxygen and/or sulfur than the phosphines, they are, in contrast to the latter, sensitive to water and hydrolyze even in the presence of small to very small amounts of moisture. Small amounts of water get into the reaction via the olefin 5 used and the synthesis gas. Owing to the recirculation of the catalyst containing the phosphites, they come into repeated contact with the water originating from the olefin and synthesis gas which results in the hydrolysis progressing and ever more phosphite being-hyd,olytically cleaved. The hydrolysis products of the phosphites no longer act as complexing agents 10 and are also no longer catalytically active.
In view of the disadvantages associated with the use of phosphites and phosphines, there is a need to provide a catalyst which does not have these disadvantages and accordingly is insensitive toward oxygen and/or 15 sulfur and, in addition, is not degraded by hydrolysis.
- The catalyst should also have sufficient hydroformylation activity and, in addition, after use be able to be reused in the hydroformylation stage without significant loss of hydroformylation activity. Furthermore, the 20 c~talyst should also withstand thermal stressing which does not occur under the conditions of the hydroformylation without suffering damage.
This is the case, for example, under the conditions of a distillation where the complexed metal carbonyls or hydridometal carbonyls formed in the hydroformylation, which presumably are the actual active catalyst, are no 25 longer stabilized by the presence of carbon monoxide and hydrogen.
In this context, attention may be drawn to the fact that the hydroformylation mixture obtained is first depressurized, usually in two stages, and excess synthesis gas is separated off and returned to the hydroformylation, if 30 appropriate after recompression.
The reaction product which has been freed of synthesis gas then goes to a multistage distillation in which the desired product is separated from the distillation residue comprising higher boilers and is then fractionally CA 022~8280 1998-12-23 distilled. The hydroformylation catalyst remains in the distillation residue.
As a result of the thermal stressing, the hydroformylation catalyst can be deactivated, for example by decomposition or precipitation of colloidal metal. However, a catalyst which has been deactivated in this way is no 5 longer suitable for reuse.
For these reasons it is also necessary for a catalyst to withstand the conditions of a distillation without significant losses in hydroformylation activity and also hydroformylation selectivity and to be able to be 10 successfully reused in the hydroformylation stage, for example as catalyst-containing distillation residue.
In addition, the catalyst should be able to be prepared without great technical difficulty and comparatively readily available starting materials 15 should be used in its preparation.
This object is achieved by a catalyst comprising rhodium and a compound of the fommula (I) R 2 (CH2) m--~ (CH2)n R (I) R~,~ (CH2) rn--~ (CH2) n I
R1/\~ \ R3 where R1, R2 and R3 are identical or different and are, independently of one another, hydrogen, an alkyl or alkoxy group having from 1 to 4 carbon atoms, an alkenyl group having from 2 to 4 carbon atoms or R1 and R2 30 together with the carbon atoms connecting them form a ring having 6 carbon atoms, m and n are, independently of one another, 0 or 1 and (m+n) is 1 or 2, and R is a phenyl or naphthyl radical which may be unsubstituted or substituted by an alkyl group having from 1 to 4 carbon atoms or an amino or dialkylamino group having a total of from 2 to 8 CA 022~8280 1998-12-23 carbon atoms.
The compound of the formula (I) is a bisether containing a 2,2'-bisaryl radical. These compounds and their preparation are subject matter of a German Patent Application (Number 19 625 167.2) filed on the same day as the present patent application.
The bisethers containing the 2,2'-bisaryl radical are stable to both oxygen and sulfur. Furthermore, they are not hydrolyzable even under the conditions of the hydroformylation. They also transmit these advantageous properties to the catalyst of the invention comprising rhodium and a compound of the formula (I).
It is surprising that the catalyst of the invention has a hydroformylation activity and hydroformylation selectivity comparable with pure rhodium, since ligand-containing rhodium catalysts usually have a significantly reduced hydroformylation activity and altered hydroformylation selectivity compared with pure rhodium.
The hydroformylation selectivity is expressed, inter alia, by the ratio in which n-aldehydes and i-aldehydes are formed and by the extent to which an isomerization of the olefinic compounds takes place, for example with migration of the carbon-carbon double bond.
The comparatively high thermal stressability of the rhodium complex catalysts, for example those described in DE-C 17 93 063, is derived from the pronounced ability of the phosphites and phosphines used to form stable complexes with rhodium. Here, the trivalent phosphorus coordinates to rhodium.
In view of this it is also surprising that the catalyst of the invention likewise has a high thermal stressability although the compound of the formula (I) contains no trivalent phosphorus. The exceptionally high thermal stressability is demonstrated by the fact that the reaction mixture formed in CA 022~8280 1998-12-23 the hydroformylation can be distilled off and the catalyst remaining in the distillation residue is not decomposed or deactivated by this procedure, but can be reused in the hydroformylation reaction.
5 Compared with an uncomplexed catalyst containing only rhodium without a ligand, the catalyst of the invention has a significantly increased stability, as is shown by the comparative examples carried out using unmodified pure rhodium (rhodium without ligand) as hydroformylation catalyst.
10 The catalyst comprises rhodium and, in particular, a compound of the formula (I) in which R1, R2 and R3 are identical or different and are, independently of one another, hydrogen, an alkyl or alkoxy group having from 1 to 2 carbon atoms or R1 and R2 together with the carbon atoms connecting them form a ring having 6 carbon atoms.
In particular, m=1 and n=0 or m=1 and n=1 in the compound of the formula (1).
In the compound of the formula (I), R is usually an unsubstituted phenyl or 20 naphthyl radical or a phenyl or naphthyl radical substituted by an alkyl group having from 1 to 4 carbon atoms, in particular an unsubstituted phenyl radical or a phenyl radical substituted by an alkyl group having from 1 to 4 carbon atoms, preferably a phenyl radical.
25 Of particular interest are catalysts in which the compound of the formula (I) corresponds to the formula (Il) or (Ill) CA 022~8280 1998-12-23 CH2 - O - (CH2) n ~ R
(Il) CH2 - O - (CH2)n ~ R
~ CH2 - O - (CH2) n- R
(Ill).
~r CH2 - O - (CH2) - R
In the compound of the formula (Il), R1 and R2 together with the carbon15 atoms of the respective benzene ring which connect them form a ring, thus forming a 1,1-binaphthyl group substituted in the 2 and 2' positions, while in the formula (Ill) R1 and R2 are hydrogen. R3 is hydrogen in both formula (Il) and formula (Ill).
20 The catalyst can be prepared in a simple manner by combining rhodium, for example in the form of a salt, with the compound of the formula (I). It is particularly useful to use the rhodium in the form of a salt soluble in an organic solvent, for example as a rhodium salt of an aliphatic carboxylic acid having from 2 to 10 carbon atoms, for example as rhodium acetate, 25 rhodium butyrate, rhodium 2-ethylhexanoate or rhodium acetylacetonate and to dissolve it together with the compound of the formula (I) in an organic solvent. It is also possible to first dissolve the rhodium salt and subsequently add the compound of the formula (I) or, the other way around, first dissolve the compound of the formula (I) and subsequently 30 add the rhodium salt.
The solvent used here should be inert under the conditions of the hydroformylation. Examples of such solvents are toluene, o-xylene, m-xylene, p-xylene, mixtures of isomeric xylenes, ethylbenzene, mesitylene or CA 022~8280 1998-12-23 intrinsic reaction products which are recirculated with the catalyst.
However, it is also possible to use the reaction product formed in the hydroformylation as solvent.
The catalyst comprising rhodium and the compound of the formula (I) can be used directly, i.e. without additional treatment, in the hydroformylation.
. , However, it is also possible to first subject the catalyst comprising rhodium 10 and the compound of the formula (I) to a pretreatment in the presence of hydrogen and carbon monoxide under pressure and possibly elevated temperature and to prepare the actual active catalyst species by means of this preactivation. The conditions for the preactivation usually correspond to the conditions of a hydroformylation.
The catalyst usually comprises rhodium and the compound of the formula (I) in a molar ratio of from 1 :1 to 1 :1000, in particular from 1 :1 to 1 :50, preferably from 1:2 to 1:20.
If a greater excess of the compound of the formula (I) is desired, the 20 catalyst can comprise rhodium and the compound of the formula (I) in a molarratioof 1:1000to 1:5000, in particularfrom 1:1000to 1:2000.
The present invention further relates to a process for the preparation of aldehydes. It comprises reacting an olefinic compound having from 2 to 20 25 carbon atoms with carbon monoxide and hydrogen in the presence of a catalyst comprising rhodium and a compound of the formula (I) R2~ (CH2) m--~ (CH2)n R (I) 1~ (CH2) m--~ (CH2) n R R
CA 022~8280 1998-12-23 where R1, R2 R3, m, n and R are as defined above, at a pressure of from 10 to 500 bar and a temperature of from 90 to 150~C.
The reaction can be carried out in the presence or absence of a solvent which is inert under the conditions of the hydroformylation. Suitable solvents are, for example, toluene, o-xylene, m-xylene, p-xylene, mixtures of isomeric xylenes, ethylbenzene, mesitylene or intrinsic reaction products which are recirculated with the catalyst. It is also possible to use mixtures of these solvents.
The reaction product formed in the hydroformylation is usually also suitable as solvent.
The olefinic compound can contain one or more than one carbon-carbon double bond. The carbon-carbon double bond can be terminal or internal.
Preference is given to olefinic compounds having a terminal carbon-carbon double bond.
Examples of ~-olefinic compounds (having a terminal carbon-carbon double bond) are alkenes, alkyl alkenoates, alkenyl alkanoates, alkenyl alkyl ethers and alkenols, in particular those having from 2 to 8 carbon atoms.
Without making any claim as to completeness, ~-olefinic compounds which may be mentioned are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-octadecene, 2-ethyl-1-hexene, styrene, 3-phenyl-1-propene, allyl chloride, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene, allyl alcohol, hex-1-en-4-ol, oct-1-en-4-ol, vinyl acetate, allyl acetate, 3-butenyl acetate, vinyl propionate, allyl propionate, allyl butyrate, methyl methacrylate, vinylcyclohexene, 3-butenyl acetate, vinyl ethyl ether, vinyl methyl ether, allyl ethyl ether, n-propyl-7-octenoate, 3-butenoic acid, 7-octenoic acid, 3-butenenitrile, 5-hexenamide.
As examples of further suitable olefinic compounds, mention may be made of 2-butene, diisobutylene, tripropylene, octol or dimersol (dimerization CA 022~8280 l998-l2-23 products of butenes), tetrapropylene, cyclohexene, cyclopentene, dicyclopentadiene, acyclic, cyclic or bicyclic terpenes such as myrcene, limonene and pinene.
5 The above-described catalyst comprising rhodium and the compound of the formula (I) is usually used in an amount of from 2x1 o-6 to 5x1 o-2 mol, in particular from 5x1 o-6 to 5x10-3 mol, preferably from 1 x10-5 to 1 x10-4 mol, of rhodium per mol of olefinic compound.
-10 The amount of rhodium also depends on the type of olefinic compound tobe hydroformylated. In some cases it may be sufficient to use the catalyst in an amount of 1 x1 o-6 mol of rhodium or less per mol of olefinic compound. Although such low catalyst concentrations are possible, in the individual case they may prove to be not particularly advantageous since 15 the reaction rate may be too low and therefore not economic enough. The upper catalyst concentration can be up to 1x1 o-1 mol of rhodium per mol of olefinic compound. However, comparatively high rhodium concentrations give no particular advantages. The upper limit is therefore set by the high cost of the rhodium.
The reaction is carried out in the presence of hydrogen and carbon monoxide. The molar ratio of hydrogen to carbon monoxide can be selected within wide limits and is usually from 1:10 to 10:1, in particular from 5:1 to 1:5, preferably from 2:1 to 1:2.
25 The process is particularly simple when hydrogen and carbon monoxide are used in a molar ratio of 1:1 or approximately 1:1.
In many cases it has been found to be useful to carry out the reaction at a pressure of from 20 to 400 bar, in particular from 100 to 250 bar.
In many cases it is sufficient to carry out the reaction at a temperature of from 100 to 1 50~C, in particular from 1 10 to 1 30~C.
At this point it may be pointed out that the reaction conditions, in particular CA 022~8280 1998-12-23 rhodium concentration, pressure and temperature, also depend on the type of olefinic compound to be hydroformylated. Comparatively reactive olefinic compounds require low rhodium concentrations, low pressures and low temperatures. In contrast, the reaction of relatively unreactive olefinic 5 compounds necessitates higher rhodium concentrations, higher pressures and higher temperatures.
The process can be carried out particularly successfully if a ~-olefinic compound is used. However, other olefinic compounds having internal 10 carbon-carbon double bonds can also be reacted with good results.
After the reaction is complete, the hydroformylation mixture is freed of carbon monoxide and hydrogen by depressurization and is subsequently distilled, with the desired product comprising the aldehydes usually being 15 distilled off via the top. The catalyst comprising rhodium and the compound of the formula (I) remains in the distillation residue and in this form can be reused in the hydroformylation reaction.
If the catalyst is recirculated a plurality of times in this way, there can result 20 an increase in high boilers which accumulate in the respective distillation residue and are returned with the catalyst to the hydroformylation.
However, these high boilers can be substantially removed by distillation under more intense conditions, for example by means of flash distillation in 25 a falling-film evaporator, without the catalyst being harmed thereby.
Such removal of high boilers can advantageously lead to a significant increase in the activity of the recirculated catalyst. In this way, the catalystcan be successfully reused a plurality of times in the hydroformylation reaction. It should be emphasized here that despite repeated recovery and 30 multiple reuse of the catalyst, the rhodium losses are barely detectable or very low.
In a particular process variant, the following procedure can be used. The reaction product obtained after the reaction with carbon monoxide and CA 022~8280 1998-12-23 hydrogen is freed of the low-boiling constituents in a first distillation stage and freed of higher-boiling thick oils in a second distillation stage under intensified distillation conditions and the catalyst-containing bottom product obtained in the second distillation stage is returned to the reaction of the 5 olefinic compound with carbon monoxide and hydrogen.
The process of the invention can be carried out continuously or batchwise, in particular continuously.
10 The following Examples illustrate the invention without restricting it.
Experimental part 15 Preparation of the catalyst The catalyst is prepared in situ from 0.073 mmol of rhodium and 0.73 mmol of 2,2'-bis(phenoxymethyl)-1,1'-binaphthyl as ligand, corresponding to a molar ratio of Rh:ligand of 1 :10, as described below for the 20 hydroformylation of propylene in Example 1.
The preparation of 2,2'-bis(phenoxymethyl)-1,1'-binaphthyl is described in the previously mentioned German Patent Application (Number 19 625 167.2) filed on the same day as the present patent application.
The formula of the 2,2'-bis(phenoxymethyl)-1,1'-binaphthyl is shown under the heading "Ligand" in the Table below.
Example 1 a) Hydroformylation of propylene A stirring autoclave (volume: 5 liters) is charged with 400 g of toluene, 0.073 mmol of rhodium in the form of 1.48 ml of a 5052.3 mg Rh/liter CA 022~8280 1998-12-23 toluene solution and 0.73 mmol (0.34 g) of 2,2'-bis(phenoxymethyl)-1,1'-binaphthyl as ligand. The autoclave is flushed thoroughly with nitrogen and synthesis gas and a pressure of 100 bar is set by adding synthesis gas (CO:H2 = 1: 1).
5 A temperature of 130~C is then set while stirring and the pressure is increased to 270 bar by addition of synthesis gas (CO:H2 = 1 :1).1500 g of propylene are then pumped in over a period of from 1 to 2 hours and the reaction is carried out at 130~C and 270 bar. The reaction proceeds exothermically. The reaction temperature is controlled by cooling the 10 autoclave by means of a blower and by the rate at which the propylene is - pumped in. After all the propylene has been pumped in, the mixture is allowed to react further. The total reaction time (pumping-in time + after-reaction time) is shown in the Table below under the heading "Time".
The autoclave is subsequently cooled to room temperature and 15 depressurized via a cold trap to from 2 to 5 bar. 6 g of liquid product are collected in the cold trap.
By means of the residual pressure, the contents of the autoclave are transferred via an immersed tube into a 61 glass flask and weighed (2763 g). From the weight increase of the combined liquid products, the 20 propylene conversion is calculated as 92%. The ratio of n-butanal:i-butanal is 52:48, determined by gas chromatography.
b) Recovery of the catalyst 25 The hydroformylation product is transferred under a blanket of N2 into a rotary evaporator and the aldehydes (n-butanal and i-butanal) are distilled off, first at 80~C and toward the end at 100~C in a water pump vacuum which is 100 mbar at first and 25 mbar toward the end of the distillation.
To complete the separation, distillation is continued for 15 minutes at 30 100~C and full water pump vacuum.
The total duration of the distillation is 2.5 hours.
The hydroformylation product obtained in Example 1 gives 47.9 g of a residue which contains the catalyst (rhodium + ligands).
CA 022~8280 1998-12-23 Examples 2 to 8 a) Hydroformylation of propylene with recycling (reuse) of the catalyst 5 The residue containing the catalyst is in each case taken up with such an amount of butyraldehyde distillate that the total amount is about 400 9 and thus gives the same level in the autoclave (volume: 5 liters) in each case, and is again transferred into the autoclave using N2 pressure.
The stirring autoclave used in Example 1 is charged with about 400 9 of 10 product (catalyst-containing residue + butyraldehyde distillate). The autoclave is thoroughly flushed with nitrogen and synthesis gas and a pressure of 100 bar is set by addition of synthesis gas (CO:H2 = 1:1).
Subsequently, a temperature of 1 30~C is set while stirring and the pressure is increased to 270 bar by addition of synthesis gas (CO:H2 = 1:1). 1500 9 of propylene are then pumped in over a period of from 1 to 2 hours and reacted at 130~C and 270 bar. The reaction proceeds exothermically.
The reaction temperature is controlled by cooling the autoclave by means 20 of a blower and by the rate at which the propylene is pumped in. After all the propylene has been pumped in, the mixture is allowed to react further.
The total reaction time (pumping-in time + after-reaction time) is shown in the following Table under the heading "Time".
25 The autoclave is subsequently cooled to room temperature and depressurized via a cold trap to from 2 to 5 bar. A small amount of product is always obtained in the cold trap. By means of the residual pressure, the contents of the autoclave are transferred via an immersed tube into a 61 glass flask and weighed.
From the weight increase of the combined liquid products, the propyleneconversion indicated in the Table below (see heading "Conversion") is calculated .
The ratio of n-butanal:i-butanal is in each case 52:48, determined by gas chromatography.
b) Recovery of the catalyst The hydroformylation product obtained in Examples 2 to 7 is transferred to a rotary evaporator and the aldehydes (n-butanal and i-butanal) are distilled off, first at 80~C and toward the end at 100~C under a water pump vacuum which is 100 mbar at first and 25 mbar toward the end of the distillation .
10 To complete the separation, distillation is continued for 15 minutes at 100~C and full water pump vacuum. The residue obtained in each case is used as catalyst in the subsequent example. The hydroformylation product obtained in Example 2 gives 151 g of residue and is used in Example 3 (2nd reuse), the hydroformylation product obtained in Example 3 gives 253 15 g of residue and is used in Example 4 (3rd reuse) and the hydroformylation product obtained in Example 4 gives 351 g of residue and is used in Example 5 (4th reuse) as catalyst (rhodium and ligand).
In the 4th reuse of the residue of 351 g, the reaction leads to a significantly 20 decreased conversion of 45%. To remove the high boilers, the hydroformylation product obtained in Example 5 (4th reuse) is subjected to a film evaporation at 100 mbar and a wall temperature of 160~C. This reduces the amount of residue containing the catalyst to 187 9.
Subsequently, in Example 6 (5th reuse), a conversion of 94% is achieved.
25 The thick oils obviously have a deactivating effect on the catalyst.
After Example 7 (6th reuse), relatively high-boiling thick oil again has to be removed by means of film evaporation at 100 mbar and a wall temperature of 160~C.
Subsequently, the residue containing the catalyst (rhodium and ligand), 30 which has been reduced to 137 g, again gives a conversion of 94% in Example 8 (7th reuse).
These results evidence the very high stability and simultaneously very high activity of the catalyst.
CA 022~8280 1998-12-23 Comparative Example 1 a) Hydroformylation of propylene using rhodium without ligand A stirring autoclave (volume: 5 liters) is, as indicated in Example 1, charged with 400 9 of toluene and 0.073 mmol of rhodium in the form of 1.48 ml of a toluene solution containing 5052.3 mg of Rh/liter, but no ligand.
Th~ reaction of propylene is subsequently carried out as described in Example 1 at 130~C and 270 bar. From the weight increase of the 10 combined liquid products (product in the cold trap + contents of the autoclave), the propylene conversion is calculated as 93% (see also the Table below).
b) Recovery of the rhodium The hydroformylation mixture is worked up as described in Example 1 b) to give 87.1 9 of a rhodium-containing residue which is used in Comparative Example 2 (1st reuse).
Comparative Examples 2 to 4 a) Hydroformylation of propylene with recycling (reuse) of the rhodium 25 The residue containing the rhodium is in each case taken up with such an amount of butyraldehyde distillate that the total amount is about 400 9 and thus gives the same level in the autoclave (volume: 5 liters) in each case, and is again transferred into the autoclave using N2 pressure. The subsequent procedure is as described in Examples 2 to 8 and the reaction 30 of propylene is carried out at 130~C and 270 bar. The total reaction time (pumping-in time + after-reaction time) is shown in the following Table under the heading "Time".
Comparative Example 2 gives a conversion of 88%, Comparative Example 3 (2nd reuse) in contrast shows a strongly reduced conversion of 39% and CA 022~8280 1998-12-23 Comparative Example 4 (3rd reuse) indicates that no more propylene at all is reacted.
Since over 90% of the rhodium is recovered, the deactivation is attributable to the absence of the ligand.
b) Recovery of the rhodium The hydroformylat,on product obtained in Comparative Examples 2 and 3 is transferred to a rotary evaporator and the aldehydes (n-butanal and i-10 butanal) are distilled off as described in Examples 2 to 8 under b)Recovery of the catalyst. The hydroformylation product obtained in Comparative Example 2 gives 293 g of rhodium-containing residue which is used in Comparative Example 3 (2nd reuse), and the hydroformylation product obtained in Comparative Example 3 gives 273 g of rhodium-15 containing residue which is used in Comparative Example 4 (3rd reuse).
The results of Examples 1 to 8 and Comparative Examples 1 to 4 areshown in the Table below.
Table: Hydroformylation of propylene using rhodium/2,2'-bis(phenoxymethyl)-1,1'-binaphthyl and rhodium (without ligand) at 270 bar of H2/CO, 130~C, 5 ppm of Rh based on propylene (_ 2.045x10-6 mol of Rh/mol of propylene) Molar ratio Rh/ligand = 1:10 Rh unmodified (without ligand) Ligand Number of reuses Examples 1 to 8 Comparative Examples 1 to 4 Conversion (%) Time (hours) Conversion (%) Time (hours) ,~ 0 92 3.3 93 3.0 OPh 1 88 3.1 88 2.8 \~ \/ 2 94 3.3 39 3.8 3 89 3.8 0 3.5 ~\ OPh 4 45~ 2.8 D
6 92- 4 1 a 7 94 3.8 O
n/i ratio~ 52/48 52148 Rhrecovery 100 93 Removal of the high boilers (aldols, carboxylic acids) by film evaporation (100 mbar and a wall temperature of 160~C) ~~ Ratio of n-butanal: i-butanal determined by gas-chromatographic analysis
WO 97/49490 T F' '~ L~ 0.~ PCT/EP97/03169 Description Catalyst and a process for the preparation of aldehydes in the presence of this catalyst The present invention relates to a novel catalyst and a process for - - preparing aldehydes by reacting olefinic compounds with carbon monoxide and hydrogen in the presence of this catalyst.
Owing to their chemical properties, aldehydes are an important group oforganic compounds. They can, for example by means of an aldol reaction with themselves or with another C-H-acid compound (methylene component), be converted into the corresponding aldols or, after 15 dehydration of the aldol, into the corresponding unsaturated condensation products. Aldehydes can also be oxidized to give the corresponding carboxylic acids or reduced to give the corresponding alcohols. Reaction of aldehydes with ammonia or amines gives imines or Schiff bases which can be reacted with hydrogen to form the corresponding amines.
Aldehydes are obtained on an industrial scale by hydroformylation of olefinic compounds. The reaction of the carbon-carbon double bonds with carbon monoxide and hydrogen results in the formation of, as shown schematically in the following reaction equation for a terminal olefin, mixtures of straight-chain and branched aldehydes.
R CH=CH2 ~ R CH CH3 + R CH2 CH2 CHO
CHO
Depending on the reaction conditions, mixtures having different compositions are obtained. In many cases, mixtures having as high as possible a proportion of straight-chain aldehydes and as low as possible a proportion of branched aldehydes are desired. Apart from the reaction CA 022~8280 1998-12-23 conditions such as pressure and temperature, the hydroformylation catalyst used exercises a decisive influence on the course of the reaction and the composition of the reaction mixture.
5 In the hydroformylation of olefins, hydroformylation catalysts which have been found to be particularly useful are rhodium catalysts containing phosphorus-containing ligands. Suitable phosphorus-containing ligands are phosphines cr phosphi'es. DE-C 17 93 069 describes such a hydro-formylation process.
However, a disadvantage is that the phosphites and in particular the phosphines are not stable toward oxygen and sulfur and are oxidized even by very small amounts of oxygen and/or sulfur, giving phosphates, thiophosphates, phosphine oxides and/or phosphine sulfides.
15 The oxygen gets into the reaction mainly via the olefin used as starting material, while the sulfur is introduced into the reaction in the form of sulfur-containing compounds, for example as H2S, via the synthesis gas.
Oxygen and/or sulfur have an adverse effect even in very small amounts 20 since after the hydroformylation is complete the catalyst is usually separated from the reaction product, for example by distillation, and reused in the hydroformylation stage. There it again comes into contact with the oxygen originating from the starting olefin and the sulfur or the sulfur-containing compound introduced with the synthesis gas. As a result, further 25 amounts of phosphite or phosphine are reacted with oxygen and/or sulfur.
The resulting phosphinic acids, thiophosphates, phosphine oxides and phosphine sulfides no longer function as complexing ligands and are thus no longer catalytically active. In addition, sulfur-containing compounds frequently have an adverse effect on catalytic processes and act as 30 catalyst poisons.
The phosphates, thiophosphates, phosphine oxides and phosphine sulfides formed are undesired in the hydroformylation and therefore have to be removed. Their removal proves, like the work-up of the catalyst, more precisely rhodium, to be difficult and is technically complicated.
CA 022~8280 1998-12-23 Although the phosphites are somewhat less sensitive to oxygen and/or sulfur than the phosphines, they are, in contrast to the latter, sensitive to water and hydrolyze even in the presence of small to very small amounts of moisture. Small amounts of water get into the reaction via the olefin 5 used and the synthesis gas. Owing to the recirculation of the catalyst containing the phosphites, they come into repeated contact with the water originating from the olefin and synthesis gas which results in the hydrolysis progressing and ever more phosphite being-hyd,olytically cleaved. The hydrolysis products of the phosphites no longer act as complexing agents 10 and are also no longer catalytically active.
In view of the disadvantages associated with the use of phosphites and phosphines, there is a need to provide a catalyst which does not have these disadvantages and accordingly is insensitive toward oxygen and/or 15 sulfur and, in addition, is not degraded by hydrolysis.
- The catalyst should also have sufficient hydroformylation activity and, in addition, after use be able to be reused in the hydroformylation stage without significant loss of hydroformylation activity. Furthermore, the 20 c~talyst should also withstand thermal stressing which does not occur under the conditions of the hydroformylation without suffering damage.
This is the case, for example, under the conditions of a distillation where the complexed metal carbonyls or hydridometal carbonyls formed in the hydroformylation, which presumably are the actual active catalyst, are no 25 longer stabilized by the presence of carbon monoxide and hydrogen.
In this context, attention may be drawn to the fact that the hydroformylation mixture obtained is first depressurized, usually in two stages, and excess synthesis gas is separated off and returned to the hydroformylation, if 30 appropriate after recompression.
The reaction product which has been freed of synthesis gas then goes to a multistage distillation in which the desired product is separated from the distillation residue comprising higher boilers and is then fractionally CA 022~8280 1998-12-23 distilled. The hydroformylation catalyst remains in the distillation residue.
As a result of the thermal stressing, the hydroformylation catalyst can be deactivated, for example by decomposition or precipitation of colloidal metal. However, a catalyst which has been deactivated in this way is no 5 longer suitable for reuse.
For these reasons it is also necessary for a catalyst to withstand the conditions of a distillation without significant losses in hydroformylation activity and also hydroformylation selectivity and to be able to be 10 successfully reused in the hydroformylation stage, for example as catalyst-containing distillation residue.
In addition, the catalyst should be able to be prepared without great technical difficulty and comparatively readily available starting materials 15 should be used in its preparation.
This object is achieved by a catalyst comprising rhodium and a compound of the fommula (I) R 2 (CH2) m--~ (CH2)n R (I) R~,~ (CH2) rn--~ (CH2) n I
R1/\~ \ R3 where R1, R2 and R3 are identical or different and are, independently of one another, hydrogen, an alkyl or alkoxy group having from 1 to 4 carbon atoms, an alkenyl group having from 2 to 4 carbon atoms or R1 and R2 30 together with the carbon atoms connecting them form a ring having 6 carbon atoms, m and n are, independently of one another, 0 or 1 and (m+n) is 1 or 2, and R is a phenyl or naphthyl radical which may be unsubstituted or substituted by an alkyl group having from 1 to 4 carbon atoms or an amino or dialkylamino group having a total of from 2 to 8 CA 022~8280 1998-12-23 carbon atoms.
The compound of the formula (I) is a bisether containing a 2,2'-bisaryl radical. These compounds and their preparation are subject matter of a German Patent Application (Number 19 625 167.2) filed on the same day as the present patent application.
The bisethers containing the 2,2'-bisaryl radical are stable to both oxygen and sulfur. Furthermore, they are not hydrolyzable even under the conditions of the hydroformylation. They also transmit these advantageous properties to the catalyst of the invention comprising rhodium and a compound of the formula (I).
It is surprising that the catalyst of the invention has a hydroformylation activity and hydroformylation selectivity comparable with pure rhodium, since ligand-containing rhodium catalysts usually have a significantly reduced hydroformylation activity and altered hydroformylation selectivity compared with pure rhodium.
The hydroformylation selectivity is expressed, inter alia, by the ratio in which n-aldehydes and i-aldehydes are formed and by the extent to which an isomerization of the olefinic compounds takes place, for example with migration of the carbon-carbon double bond.
The comparatively high thermal stressability of the rhodium complex catalysts, for example those described in DE-C 17 93 063, is derived from the pronounced ability of the phosphites and phosphines used to form stable complexes with rhodium. Here, the trivalent phosphorus coordinates to rhodium.
In view of this it is also surprising that the catalyst of the invention likewise has a high thermal stressability although the compound of the formula (I) contains no trivalent phosphorus. The exceptionally high thermal stressability is demonstrated by the fact that the reaction mixture formed in CA 022~8280 1998-12-23 the hydroformylation can be distilled off and the catalyst remaining in the distillation residue is not decomposed or deactivated by this procedure, but can be reused in the hydroformylation reaction.
5 Compared with an uncomplexed catalyst containing only rhodium without a ligand, the catalyst of the invention has a significantly increased stability, as is shown by the comparative examples carried out using unmodified pure rhodium (rhodium without ligand) as hydroformylation catalyst.
10 The catalyst comprises rhodium and, in particular, a compound of the formula (I) in which R1, R2 and R3 are identical or different and are, independently of one another, hydrogen, an alkyl or alkoxy group having from 1 to 2 carbon atoms or R1 and R2 together with the carbon atoms connecting them form a ring having 6 carbon atoms.
In particular, m=1 and n=0 or m=1 and n=1 in the compound of the formula (1).
In the compound of the formula (I), R is usually an unsubstituted phenyl or 20 naphthyl radical or a phenyl or naphthyl radical substituted by an alkyl group having from 1 to 4 carbon atoms, in particular an unsubstituted phenyl radical or a phenyl radical substituted by an alkyl group having from 1 to 4 carbon atoms, preferably a phenyl radical.
25 Of particular interest are catalysts in which the compound of the formula (I) corresponds to the formula (Il) or (Ill) CA 022~8280 1998-12-23 CH2 - O - (CH2) n ~ R
(Il) CH2 - O - (CH2)n ~ R
~ CH2 - O - (CH2) n- R
(Ill).
~r CH2 - O - (CH2) - R
In the compound of the formula (Il), R1 and R2 together with the carbon15 atoms of the respective benzene ring which connect them form a ring, thus forming a 1,1-binaphthyl group substituted in the 2 and 2' positions, while in the formula (Ill) R1 and R2 are hydrogen. R3 is hydrogen in both formula (Il) and formula (Ill).
20 The catalyst can be prepared in a simple manner by combining rhodium, for example in the form of a salt, with the compound of the formula (I). It is particularly useful to use the rhodium in the form of a salt soluble in an organic solvent, for example as a rhodium salt of an aliphatic carboxylic acid having from 2 to 10 carbon atoms, for example as rhodium acetate, 25 rhodium butyrate, rhodium 2-ethylhexanoate or rhodium acetylacetonate and to dissolve it together with the compound of the formula (I) in an organic solvent. It is also possible to first dissolve the rhodium salt and subsequently add the compound of the formula (I) or, the other way around, first dissolve the compound of the formula (I) and subsequently 30 add the rhodium salt.
The solvent used here should be inert under the conditions of the hydroformylation. Examples of such solvents are toluene, o-xylene, m-xylene, p-xylene, mixtures of isomeric xylenes, ethylbenzene, mesitylene or CA 022~8280 1998-12-23 intrinsic reaction products which are recirculated with the catalyst.
However, it is also possible to use the reaction product formed in the hydroformylation as solvent.
The catalyst comprising rhodium and the compound of the formula (I) can be used directly, i.e. without additional treatment, in the hydroformylation.
. , However, it is also possible to first subject the catalyst comprising rhodium 10 and the compound of the formula (I) to a pretreatment in the presence of hydrogen and carbon monoxide under pressure and possibly elevated temperature and to prepare the actual active catalyst species by means of this preactivation. The conditions for the preactivation usually correspond to the conditions of a hydroformylation.
The catalyst usually comprises rhodium and the compound of the formula (I) in a molar ratio of from 1 :1 to 1 :1000, in particular from 1 :1 to 1 :50, preferably from 1:2 to 1:20.
If a greater excess of the compound of the formula (I) is desired, the 20 catalyst can comprise rhodium and the compound of the formula (I) in a molarratioof 1:1000to 1:5000, in particularfrom 1:1000to 1:2000.
The present invention further relates to a process for the preparation of aldehydes. It comprises reacting an olefinic compound having from 2 to 20 25 carbon atoms with carbon monoxide and hydrogen in the presence of a catalyst comprising rhodium and a compound of the formula (I) R2~ (CH2) m--~ (CH2)n R (I) 1~ (CH2) m--~ (CH2) n R R
CA 022~8280 1998-12-23 where R1, R2 R3, m, n and R are as defined above, at a pressure of from 10 to 500 bar and a temperature of from 90 to 150~C.
The reaction can be carried out in the presence or absence of a solvent which is inert under the conditions of the hydroformylation. Suitable solvents are, for example, toluene, o-xylene, m-xylene, p-xylene, mixtures of isomeric xylenes, ethylbenzene, mesitylene or intrinsic reaction products which are recirculated with the catalyst. It is also possible to use mixtures of these solvents.
The reaction product formed in the hydroformylation is usually also suitable as solvent.
The olefinic compound can contain one or more than one carbon-carbon double bond. The carbon-carbon double bond can be terminal or internal.
Preference is given to olefinic compounds having a terminal carbon-carbon double bond.
Examples of ~-olefinic compounds (having a terminal carbon-carbon double bond) are alkenes, alkyl alkenoates, alkenyl alkanoates, alkenyl alkyl ethers and alkenols, in particular those having from 2 to 8 carbon atoms.
Without making any claim as to completeness, ~-olefinic compounds which may be mentioned are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-octadecene, 2-ethyl-1-hexene, styrene, 3-phenyl-1-propene, allyl chloride, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene, allyl alcohol, hex-1-en-4-ol, oct-1-en-4-ol, vinyl acetate, allyl acetate, 3-butenyl acetate, vinyl propionate, allyl propionate, allyl butyrate, methyl methacrylate, vinylcyclohexene, 3-butenyl acetate, vinyl ethyl ether, vinyl methyl ether, allyl ethyl ether, n-propyl-7-octenoate, 3-butenoic acid, 7-octenoic acid, 3-butenenitrile, 5-hexenamide.
As examples of further suitable olefinic compounds, mention may be made of 2-butene, diisobutylene, tripropylene, octol or dimersol (dimerization CA 022~8280 l998-l2-23 products of butenes), tetrapropylene, cyclohexene, cyclopentene, dicyclopentadiene, acyclic, cyclic or bicyclic terpenes such as myrcene, limonene and pinene.
5 The above-described catalyst comprising rhodium and the compound of the formula (I) is usually used in an amount of from 2x1 o-6 to 5x1 o-2 mol, in particular from 5x1 o-6 to 5x10-3 mol, preferably from 1 x10-5 to 1 x10-4 mol, of rhodium per mol of olefinic compound.
-10 The amount of rhodium also depends on the type of olefinic compound tobe hydroformylated. In some cases it may be sufficient to use the catalyst in an amount of 1 x1 o-6 mol of rhodium or less per mol of olefinic compound. Although such low catalyst concentrations are possible, in the individual case they may prove to be not particularly advantageous since 15 the reaction rate may be too low and therefore not economic enough. The upper catalyst concentration can be up to 1x1 o-1 mol of rhodium per mol of olefinic compound. However, comparatively high rhodium concentrations give no particular advantages. The upper limit is therefore set by the high cost of the rhodium.
The reaction is carried out in the presence of hydrogen and carbon monoxide. The molar ratio of hydrogen to carbon monoxide can be selected within wide limits and is usually from 1:10 to 10:1, in particular from 5:1 to 1:5, preferably from 2:1 to 1:2.
25 The process is particularly simple when hydrogen and carbon monoxide are used in a molar ratio of 1:1 or approximately 1:1.
In many cases it has been found to be useful to carry out the reaction at a pressure of from 20 to 400 bar, in particular from 100 to 250 bar.
In many cases it is sufficient to carry out the reaction at a temperature of from 100 to 1 50~C, in particular from 1 10 to 1 30~C.
At this point it may be pointed out that the reaction conditions, in particular CA 022~8280 1998-12-23 rhodium concentration, pressure and temperature, also depend on the type of olefinic compound to be hydroformylated. Comparatively reactive olefinic compounds require low rhodium concentrations, low pressures and low temperatures. In contrast, the reaction of relatively unreactive olefinic 5 compounds necessitates higher rhodium concentrations, higher pressures and higher temperatures.
The process can be carried out particularly successfully if a ~-olefinic compound is used. However, other olefinic compounds having internal 10 carbon-carbon double bonds can also be reacted with good results.
After the reaction is complete, the hydroformylation mixture is freed of carbon monoxide and hydrogen by depressurization and is subsequently distilled, with the desired product comprising the aldehydes usually being 15 distilled off via the top. The catalyst comprising rhodium and the compound of the formula (I) remains in the distillation residue and in this form can be reused in the hydroformylation reaction.
If the catalyst is recirculated a plurality of times in this way, there can result 20 an increase in high boilers which accumulate in the respective distillation residue and are returned with the catalyst to the hydroformylation.
However, these high boilers can be substantially removed by distillation under more intense conditions, for example by means of flash distillation in 25 a falling-film evaporator, without the catalyst being harmed thereby.
Such removal of high boilers can advantageously lead to a significant increase in the activity of the recirculated catalyst. In this way, the catalystcan be successfully reused a plurality of times in the hydroformylation reaction. It should be emphasized here that despite repeated recovery and 30 multiple reuse of the catalyst, the rhodium losses are barely detectable or very low.
In a particular process variant, the following procedure can be used. The reaction product obtained after the reaction with carbon monoxide and CA 022~8280 1998-12-23 hydrogen is freed of the low-boiling constituents in a first distillation stage and freed of higher-boiling thick oils in a second distillation stage under intensified distillation conditions and the catalyst-containing bottom product obtained in the second distillation stage is returned to the reaction of the 5 olefinic compound with carbon monoxide and hydrogen.
The process of the invention can be carried out continuously or batchwise, in particular continuously.
10 The following Examples illustrate the invention without restricting it.
Experimental part 15 Preparation of the catalyst The catalyst is prepared in situ from 0.073 mmol of rhodium and 0.73 mmol of 2,2'-bis(phenoxymethyl)-1,1'-binaphthyl as ligand, corresponding to a molar ratio of Rh:ligand of 1 :10, as described below for the 20 hydroformylation of propylene in Example 1.
The preparation of 2,2'-bis(phenoxymethyl)-1,1'-binaphthyl is described in the previously mentioned German Patent Application (Number 19 625 167.2) filed on the same day as the present patent application.
The formula of the 2,2'-bis(phenoxymethyl)-1,1'-binaphthyl is shown under the heading "Ligand" in the Table below.
Example 1 a) Hydroformylation of propylene A stirring autoclave (volume: 5 liters) is charged with 400 g of toluene, 0.073 mmol of rhodium in the form of 1.48 ml of a 5052.3 mg Rh/liter CA 022~8280 1998-12-23 toluene solution and 0.73 mmol (0.34 g) of 2,2'-bis(phenoxymethyl)-1,1'-binaphthyl as ligand. The autoclave is flushed thoroughly with nitrogen and synthesis gas and a pressure of 100 bar is set by adding synthesis gas (CO:H2 = 1: 1).
5 A temperature of 130~C is then set while stirring and the pressure is increased to 270 bar by addition of synthesis gas (CO:H2 = 1 :1).1500 g of propylene are then pumped in over a period of from 1 to 2 hours and the reaction is carried out at 130~C and 270 bar. The reaction proceeds exothermically. The reaction temperature is controlled by cooling the 10 autoclave by means of a blower and by the rate at which the propylene is - pumped in. After all the propylene has been pumped in, the mixture is allowed to react further. The total reaction time (pumping-in time + after-reaction time) is shown in the Table below under the heading "Time".
The autoclave is subsequently cooled to room temperature and 15 depressurized via a cold trap to from 2 to 5 bar. 6 g of liquid product are collected in the cold trap.
By means of the residual pressure, the contents of the autoclave are transferred via an immersed tube into a 61 glass flask and weighed (2763 g). From the weight increase of the combined liquid products, the 20 propylene conversion is calculated as 92%. The ratio of n-butanal:i-butanal is 52:48, determined by gas chromatography.
b) Recovery of the catalyst 25 The hydroformylation product is transferred under a blanket of N2 into a rotary evaporator and the aldehydes (n-butanal and i-butanal) are distilled off, first at 80~C and toward the end at 100~C in a water pump vacuum which is 100 mbar at first and 25 mbar toward the end of the distillation.
To complete the separation, distillation is continued for 15 minutes at 30 100~C and full water pump vacuum.
The total duration of the distillation is 2.5 hours.
The hydroformylation product obtained in Example 1 gives 47.9 g of a residue which contains the catalyst (rhodium + ligands).
CA 022~8280 1998-12-23 Examples 2 to 8 a) Hydroformylation of propylene with recycling (reuse) of the catalyst 5 The residue containing the catalyst is in each case taken up with such an amount of butyraldehyde distillate that the total amount is about 400 9 and thus gives the same level in the autoclave (volume: 5 liters) in each case, and is again transferred into the autoclave using N2 pressure.
The stirring autoclave used in Example 1 is charged with about 400 9 of 10 product (catalyst-containing residue + butyraldehyde distillate). The autoclave is thoroughly flushed with nitrogen and synthesis gas and a pressure of 100 bar is set by addition of synthesis gas (CO:H2 = 1:1).
Subsequently, a temperature of 1 30~C is set while stirring and the pressure is increased to 270 bar by addition of synthesis gas (CO:H2 = 1:1). 1500 9 of propylene are then pumped in over a period of from 1 to 2 hours and reacted at 130~C and 270 bar. The reaction proceeds exothermically.
The reaction temperature is controlled by cooling the autoclave by means 20 of a blower and by the rate at which the propylene is pumped in. After all the propylene has been pumped in, the mixture is allowed to react further.
The total reaction time (pumping-in time + after-reaction time) is shown in the following Table under the heading "Time".
25 The autoclave is subsequently cooled to room temperature and depressurized via a cold trap to from 2 to 5 bar. A small amount of product is always obtained in the cold trap. By means of the residual pressure, the contents of the autoclave are transferred via an immersed tube into a 61 glass flask and weighed.
From the weight increase of the combined liquid products, the propyleneconversion indicated in the Table below (see heading "Conversion") is calculated .
The ratio of n-butanal:i-butanal is in each case 52:48, determined by gas chromatography.
b) Recovery of the catalyst The hydroformylation product obtained in Examples 2 to 7 is transferred to a rotary evaporator and the aldehydes (n-butanal and i-butanal) are distilled off, first at 80~C and toward the end at 100~C under a water pump vacuum which is 100 mbar at first and 25 mbar toward the end of the distillation .
10 To complete the separation, distillation is continued for 15 minutes at 100~C and full water pump vacuum. The residue obtained in each case is used as catalyst in the subsequent example. The hydroformylation product obtained in Example 2 gives 151 g of residue and is used in Example 3 (2nd reuse), the hydroformylation product obtained in Example 3 gives 253 15 g of residue and is used in Example 4 (3rd reuse) and the hydroformylation product obtained in Example 4 gives 351 g of residue and is used in Example 5 (4th reuse) as catalyst (rhodium and ligand).
In the 4th reuse of the residue of 351 g, the reaction leads to a significantly 20 decreased conversion of 45%. To remove the high boilers, the hydroformylation product obtained in Example 5 (4th reuse) is subjected to a film evaporation at 100 mbar and a wall temperature of 160~C. This reduces the amount of residue containing the catalyst to 187 9.
Subsequently, in Example 6 (5th reuse), a conversion of 94% is achieved.
25 The thick oils obviously have a deactivating effect on the catalyst.
After Example 7 (6th reuse), relatively high-boiling thick oil again has to be removed by means of film evaporation at 100 mbar and a wall temperature of 160~C.
Subsequently, the residue containing the catalyst (rhodium and ligand), 30 which has been reduced to 137 g, again gives a conversion of 94% in Example 8 (7th reuse).
These results evidence the very high stability and simultaneously very high activity of the catalyst.
CA 022~8280 1998-12-23 Comparative Example 1 a) Hydroformylation of propylene using rhodium without ligand A stirring autoclave (volume: 5 liters) is, as indicated in Example 1, charged with 400 9 of toluene and 0.073 mmol of rhodium in the form of 1.48 ml of a toluene solution containing 5052.3 mg of Rh/liter, but no ligand.
Th~ reaction of propylene is subsequently carried out as described in Example 1 at 130~C and 270 bar. From the weight increase of the 10 combined liquid products (product in the cold trap + contents of the autoclave), the propylene conversion is calculated as 93% (see also the Table below).
b) Recovery of the rhodium The hydroformylation mixture is worked up as described in Example 1 b) to give 87.1 9 of a rhodium-containing residue which is used in Comparative Example 2 (1st reuse).
Comparative Examples 2 to 4 a) Hydroformylation of propylene with recycling (reuse) of the rhodium 25 The residue containing the rhodium is in each case taken up with such an amount of butyraldehyde distillate that the total amount is about 400 9 and thus gives the same level in the autoclave (volume: 5 liters) in each case, and is again transferred into the autoclave using N2 pressure. The subsequent procedure is as described in Examples 2 to 8 and the reaction 30 of propylene is carried out at 130~C and 270 bar. The total reaction time (pumping-in time + after-reaction time) is shown in the following Table under the heading "Time".
Comparative Example 2 gives a conversion of 88%, Comparative Example 3 (2nd reuse) in contrast shows a strongly reduced conversion of 39% and CA 022~8280 1998-12-23 Comparative Example 4 (3rd reuse) indicates that no more propylene at all is reacted.
Since over 90% of the rhodium is recovered, the deactivation is attributable to the absence of the ligand.
b) Recovery of the rhodium The hydroformylat,on product obtained in Comparative Examples 2 and 3 is transferred to a rotary evaporator and the aldehydes (n-butanal and i-10 butanal) are distilled off as described in Examples 2 to 8 under b)Recovery of the catalyst. The hydroformylation product obtained in Comparative Example 2 gives 293 g of rhodium-containing residue which is used in Comparative Example 3 (2nd reuse), and the hydroformylation product obtained in Comparative Example 3 gives 273 g of rhodium-15 containing residue which is used in Comparative Example 4 (3rd reuse).
The results of Examples 1 to 8 and Comparative Examples 1 to 4 areshown in the Table below.
Table: Hydroformylation of propylene using rhodium/2,2'-bis(phenoxymethyl)-1,1'-binaphthyl and rhodium (without ligand) at 270 bar of H2/CO, 130~C, 5 ppm of Rh based on propylene (_ 2.045x10-6 mol of Rh/mol of propylene) Molar ratio Rh/ligand = 1:10 Rh unmodified (without ligand) Ligand Number of reuses Examples 1 to 8 Comparative Examples 1 to 4 Conversion (%) Time (hours) Conversion (%) Time (hours) ,~ 0 92 3.3 93 3.0 OPh 1 88 3.1 88 2.8 \~ \/ 2 94 3.3 39 3.8 3 89 3.8 0 3.5 ~\ OPh 4 45~ 2.8 D
6 92- 4 1 a 7 94 3.8 O
n/i ratio~ 52/48 52148 Rhrecovery 100 93 Removal of the high boilers (aldols, carboxylic acids) by film evaporation (100 mbar and a wall temperature of 160~C) ~~ Ratio of n-butanal: i-butanal determined by gas-chromatographic analysis
Claims (13)
1. A catalyst comprising rhodium and a compound of the formula (I) where R1, R2 and R3 are identical or different and are, independently of one another, hydrogen, an alkyl or alkoxy group having from 1 to 4 carbon atoms, an alkenyl group having from 2 to 4 carbon atoms or R1 and R2 together with the carbon atoms connecting them form a ring having 6 carbon atoms, m and n are, independently of one another, 0 or 1 and (m+n) is 1 or 2, and R is a phenyl or naphthyl radical which may be unsubstituted or substituted by an alkyl group having from 1 to 4 carbon atoms or an amino or dialkylamino group having a total of from 2 to 8 carbon atoms.
2. A catalyst as claimed in claim 1, wherein R1, R2 and R3 are identical or different and are, independently of one another, hydrogen, an alkyl or alkoxy group having from 1 to 2 carbon atoms or R1 and R2 together with the carbon atoms connecting them form a ring having 6 carbon atoms.
3. A catalyst as claimed in claim 1 or 2, wherein m=1 and n=0 or m=1 and n=1.
4. A catalyst as claimed in one or more of claims 1 to 3, wherein R is an unsubstituted phenyl or naphthyl radical or a phenyl or naphthyl radical substituted by an alkyl group having from 1 to 4 carbon atoms.
5. A catalyst as claimed in one or more of claims 1 to 4, wherein R is an unsubstituted phenyl radical or a phenyl radical substituted by an alkyl group having from 1 to 4 carbon atoms.
6. A catalyst as claimed in one or more of claims 1 to 5, wherein R is a phenyl radical.
7. A catalyst as claimed in one or more of claims 1 to 6, wherein the compound of the formula (I) corresponds to the formula (II) or (III) where n and R are as defined above.
8. A catalyst as claimed in one or more of claims 1 to 7 comprising rhodium and the compound of the formula (I) in a molar ratio of from 1:1 to 1:1000.
9. A catalyst as claimed in one or more of claims 1 to 8 comprising rhodium and the compound of the formula (I) in a molar ratio of 1:2 to 1:20.
10. A process for the preparation of aldehydes, which comprises reacting an olefinic compound having from 2 to 20 carbon atoms with carbon monoxide and hydrogen in the presence of a catalyst comprising rhodium and a compound of the formula (I) where R1, R2, R3, m, n and R are as defined above, at a pressure of from 10 to 500 bar and a temperature of from 90 to 150°C.
11. The process as claimed in claim 10, wherein an ~-olefinic compound is used.
12. The process as claimed in claim 10 or 11, wherein the catalyst is used in an amount corresponding to from 2x10-6 to 5x10-2 mol of rhodium per mol of olefinic compound.
13. The process as claimed in one or more of claims 10 to 12, wherein the reaction product obtained after reaction with carbon monoxide and hydrogen is freed of the low-boiling constituents in a first distillation stage and freed of higher-boiling thick oils in a second distillation stage under intensified distillation conditions and the catalyst-containing bottom product obtained in the second distillation stage is returned to the reaction of the olefinic compound with carbon monoxide and hydrogen.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19625168.0 | 1996-06-24 | ||
| DE19625168A DE19625168A1 (en) | 1996-06-24 | 1996-06-24 | Re-usable rhodium catalyst containing ligand resistant to oxygen, |
| PCT/EP1997/003169 WO1997049490A1 (en) | 1996-06-24 | 1997-06-18 | Catalyst and a process for preparation of aldehydes in the presence of said catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2258280A1 true CA2258280A1 (en) | 1997-12-31 |
Family
ID=7797809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002258280A Abandoned CA2258280A1 (en) | 1996-06-24 | 1997-06-18 | Catalyst and a process for preparation of aldehydes in the presence of said catalyst |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0909218A1 (en) |
| JP (1) | JP2001502594A (en) |
| KR (1) | KR20000022119A (en) |
| AU (1) | AU3340197A (en) |
| BR (1) | BR9709955A (en) |
| CA (1) | CA2258280A1 (en) |
| DE (2) | DE19654908A1 (en) |
| ID (1) | ID17186A (en) |
| PL (1) | PL330789A1 (en) |
| TW (1) | TW372199B (en) |
| WO (1) | WO1997049490A1 (en) |
| ZA (1) | ZA975540B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6573409B1 (en) | 1999-07-02 | 2003-06-03 | The Nutrasweet Company | Process for the preparation of 3,3-dimethylbutanal |
| AU2003253389A1 (en) * | 2002-08-31 | 2004-03-19 | Oxeno Olefinchemie Gmbh | Method for the hydroformylation of olefinically unsaturated compounds, especially olefins, in the presence of cyclic carbonic acid esters |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960949A (en) * | 1988-12-22 | 1990-10-02 | Eastman Kodak Company | Low pressure rhodium catalyzed hydroformylation of olefins |
| DE4242723A1 (en) * | 1992-12-17 | 1994-06-23 | Hoechst Ag | Process for the preparation of aldehydes |
| DE4447067A1 (en) * | 1994-12-29 | 1996-07-04 | Hoechst Ag | Process for the preparation of aldehydes |
-
1996
- 1996-06-24 DE DE19654908A patent/DE19654908A1/en not_active Withdrawn
- 1996-06-24 DE DE19625168A patent/DE19625168A1/en not_active Withdrawn
-
1997
- 1997-06-18 PL PL97330789A patent/PL330789A1/en unknown
- 1997-06-18 EP EP97929208A patent/EP0909218A1/en not_active Withdrawn
- 1997-06-18 CA CA002258280A patent/CA2258280A1/en not_active Abandoned
- 1997-06-18 KR KR1019980710533A patent/KR20000022119A/en not_active Application Discontinuation
- 1997-06-18 AU AU33401/97A patent/AU3340197A/en not_active Abandoned
- 1997-06-18 JP JP10502267A patent/JP2001502594A/en active Pending
- 1997-06-18 BR BR9709955A patent/BR9709955A/en not_active Application Discontinuation
- 1997-06-18 WO PCT/EP1997/003169 patent/WO1997049490A1/en not_active Application Discontinuation
- 1997-06-20 TW TW086108670A patent/TW372199B/en active
- 1997-06-23 ZA ZA9705540A patent/ZA975540B/en unknown
- 1997-06-23 ID IDP972159A patent/ID17186A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR20000022119A (en) | 2000-04-25 |
| TW372199B (en) | 1999-10-21 |
| ZA975540B (en) | 1997-12-24 |
| ID17186A (en) | 1997-12-11 |
| JP2001502594A (en) | 2001-02-27 |
| BR9709955A (en) | 1999-08-10 |
| PL330789A1 (en) | 1999-06-07 |
| AU3340197A (en) | 1998-01-14 |
| DE19625168A1 (en) | 1998-01-08 |
| WO1997049490A1 (en) | 1997-12-31 |
| EP0909218A1 (en) | 1999-04-21 |
| DE19654908A1 (en) | 1998-01-29 |
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