TW201545814A - Immobilized catalytically active composition having tridentate phosphorus ligands in an ionic liquid for hydroformylation of olefin-containing mixtures - Google Patents

Abstract

The present invention is directed to a composition comprising: (a) at least one support material; (b) at least one ionic liquid; (c) at least one metal selected from transition group VIII of the Periodic Table of the Elements; (d) at least one organic phosphorus compound having the structural element of the formula (I): and; (e) optionally one or more organic amines. The invention further encompasses a process for preparing such a composition, the use of the composition as catalytically active composition and a process for hydroformylation, in which the composition is used as catalytically active composition.

Description

Immobilized catalytically active composition having a tridentate phosphorus gamete for hydroformylation of an olefin-containing mixture in an ionic liquid

The invention relates to a composition comprising: a) at least one support material; b) at least one metal selected from the group consisting of transitions of Group VIII of the Periodic Table of Elements; and c) at least one compound having structural elements of formula (I): d) at least one ionic liquid. The invention further comprises a process for the preparation of the composition, the use of the composition as a catalytically active composition and a process for hydroformylation, wherein the composition acts as a catalytically active composition.

The reaction of an olefin compound, carbon monoxide and hydrogen in the presence of a catalyst to obtain an aldehyde having one more carbon atom is called a hydroformylation or a pendant oxy group method (Reaction Figure 1). The catalysts used in these reactions are often transition metal compounds of Group VIII of the Periodic Table of the Elements, especially rhodium or cobalt catalysts. Known gametes are, for example, compounds from the phosphine, phosphite and phosphonite classes, each having a trivalent phosphorus P ^III . A good review of the hydroformylation state of olefins can be found in B. CORNILS, WAHERRMANN, "Applied Homogeneous Catalysis with Organometallic Compounds", vol. 1 & 2, VCH, Weinheim, New York, 1996 or R. Franke, D. Selent, A. Börner, "Applied Hydroformylation", Chem. Rev., 2012, DOI: 10.1021/cr 3001803.

The starting point for the novel hydroformylation process is the concept of immobilizing a rhodium-containing catalyst system which was previously in a homogeneous form in the reaction mixture. This heterogeneous reaction, which can be referred to as a reaction, is carried out homogeneously in principle - in this case, the industrially important hydroformylation reaction is carried out homogeneously.

In the industrial scale of hydrogen methylation, not only normal / heterogeneous choice And the service life of the catalyst is also extremely important. Each exchange of catalysts requires the manufacturing plant to have a conversion time when the manufacturing plant is not operational. During this period, the manufacturing plant was unable to produce. It is an object of the present invention to develop a process by which a catalytically active composition comprising one or more catalysts (composited on a support material and eliminating the addition of other components) can be used to smoothly remove the catalyst, and simultaneously with the previous The system described in the art has an improved catalyst life in comparison. Furthermore, the useful life of the catalyst of this catalytically active composition needs to be improved, since multiple catalyst exchanges during one year of operation can be uneconomical and infeasible for the above reasons.

The sulphuric acid-based subsystem is used in homogeneous catalyzed hydrogen formazanization reactions, including high normal selectivity and improved stability to intrinsic catalyst poisons, for example from hydroformamidine reactions. Water in the aldol condensation of the formed aldehyde (DE 10 2011 085 883 A1). However, it is desirable to homogenize the system so that the catalyst can be separated.

It is therefore an object of the present invention to provide a catalyst system for hydroformylation of unsaturated compounds comprising one or more of the desirable features described above.

More particularly, it is an object of the present invention to provide a process which is capable of smoothly removing a catalyst and isomerizing an unsaturated compound and hydroformylating to an n-terminal aldehyde, and preferably simultaneously with the system described in the prior art. Compared to an improved catalyst life.

Unexpectedly, this purpose can be borrowed according to item 1 of the scope of patent application. The composition is achieved by a composition comprising a catalyst complex dissolved in an ionic liquid and on a support material, referred to as a SILP phase, the complex comprising a tridentate phosphorus gamete.

It is particularly surprising in this respect that the object is achieved by a phosphorus-containing organic compound having a structural element of the formula (I), a quinone triol substructure.

The organophosphorus compound used in the composition of the present invention and comprising the structural element of the above formula (I) - ninhydrin substructure - does not have the prior art such as Rhodium-catalyzed Hydroformylation, ed. by PWNMvan Leeuwen and C. Claver, Disadvantages described in Kluwer Academic Publishers 2006, AA Dordrecht, NL, pages 45-46. In contrast to the phosphites described in the prior art, the compositions of the invention have an apparently optimum catalyst life and therefore a significant degree of stability.

It is worth noting that these gametes in the catalyst composite (dissolved in the ionic liquid on the support material) contain excellent properties. Since these gametes are significantly greater in terms of their molecular weight than previously disclosed in the prior art All gametes and three phosphorus atoms with binding effects replace two or one phosphorus atom, so accidentally this class of gametes provides excellent selectivity and catalyst life, even in SILP phase applications.

An organophosphorus compound having a structural element of the formula (I), a ninhydrin substructure, is disclosed in DE 10 2011 085 883 A1. In the context of the present application, the contents of the specification of DE 10 2011 085 883 A1 are fully referred to.

The compositions of the present invention and their uses are exemplified in the following examples, and the invention is not intended to be limited to the illustrated embodiments. When a range, formula or class of compounds is specified below, these should include not only the corresponding ranges or groups of compounds specifically mentioned, but also all sub-ranges and sub-ranges that can be obtained by removing individual values (ranges) or compounds. group. When a document is cited in the context of the present specification, its content, particularly with regard to the subject matter in which the document is recited to form a context, is considered to be part of the overall terrain cost of the description of the invention. Percentages are expressed in weight percent unless otherwise specified. When the average is reported below, the values in the discussion are weight averages unless otherwise specified. When the parameters determined by the measurement method are reported below, they are measured at a temperature of 25 ° C and a pressure of 101 325 Pa unless otherwise specified.

Figure 1: Conversion/time diagram (□) and normal/isomeric selectivity (◇) of C4 hydroformylation with Rh(17) catalyst, parameters: m _cat = 12 g, m _Rh = 0.2 wt%, L/Rh=10, T=393.15K; p=1MPa; C4 mixture: 0-478 hours: reactant mixture A, 478-2150 hours reactant mixture B (see Table 1); H ₂ /1-butene ratio = 8; residence time: 43 seconds. For the sake of clarity, only measurements every 20 times are shown.

Figure 2: Conversion/time diagram (■) and normal/isomeric selectivity (♦) of C4 hydroformylation with Rh(17) catalyst, parameter: m _cat = 12 g, m _Rh = 0.2 wt%, L/Rh=10,×,○:T=373.15-393.15K; p=1MPa; C4-mixture: reactant mixture C (see Table 1); H ₂ /1-butene ratio=8 retention time: 43 seconds . For the sake of clarity, only the measurements obtained every 10 times are shown.

The term "inert" in the context of the present invention of course means the nature of the substance, component or mixture which does not result in an adverse effect or an effect opposite to the intended reaction process.

The composition of the invention is characterized in that it comprises: a) at least one support material, preferably porous; b) at least one ionic liquid; c) at least one metal selected from the transition group of Group VIII of the Periodic Table of the Elements; At least one organophosphorus compound comprising structural elements of formula (I):

Wherein the compound comprises at least two OP ^III bonds, which may be derived from the same P ^III or from different P ^III ; wherein, if structural element (I) is present twice in the compound, they are each via C10-C10 'Carbon bond or via the following X ¹ -G ¹ -X ² unit: -X ¹ -G ¹ -X ² -

Wherein X ^{1 is} bonded to P ^III in the first structural element (I), and X ^{2 is} bonded to P ^III in the second structural element (I), and G ¹ = linear or branched, aliphatic or aromatic a family or heteroaromatic or fused aromatic or fused aromatic-heteroaromatic hydrocarbon group, and containing any other desired substituent; wherein X ¹ , X ^{2 is} selected from the group consisting of: O, NY ¹ , CY ² Y ³ ; The definitions of ¹ and X ² may be independently selected; wherein Y ¹ , Y ² , Y ^{3 are} selected from: hydrogen, unsubstituted or substituted aliphatic or unsubstituted or substituted aromatic hydrocarbon groups; wherein Y ^{1 is} The definition of Y ³ may be independently selected; wherein two or more of Y ¹ to Y ³ may be covalently linked to each other; wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ^{7 are} selected From: hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon groups; F, Cl, Br, I, -OR ⁸ , -C(O)R ⁹ , -CO ₂ R ¹⁰ , -CO ₂ M ¹ , -SR ¹¹ , -SOR ¹² , -SO ₂ R ¹³ , -SO ₃ R ¹⁴ , -SO ₃ M ² , -NR ¹⁵ R ¹⁶ ; wherein R ⁸ , R ⁹ , R ¹⁰ , R ^{11 , R 12, R 13, R} 14, R 15, R 16 is selected from: hydrogen, substituted or unsubstituted, linear or branched, aliphatic or aromatic or heteroaromatic Fused aromatic or fused aromatic - aromatic hydrocarbon heteroaryl; -OR ^17; wherein R ¹⁷ is selected from: hydrogen, substituted or unsubstituted, linear or branched, aliphatic or aromatic hydrocarbon group; in which R ¹ And two or more of R ¹⁷ may be covalently linked to each other; wherein M ¹ and M ^{2 are} selected from the group consisting of alkali metal, alkaline earth metal, ammonium, cerium, and wherein the definitions of M ¹ and M ² are independently selected; e) Optionally one or more organic amines.

All of the support material can be any known support material, preferably a porous support material. Preferably, the porous support material used is inert to the other components of the composition and to the co-reactants and reaction products of the reaction using the composition. The preferred support material is inorganic, preferably an oxidized support material. Suitable support materials are, in particular, aluminum oxides, cerium oxides, titanium oxides or zirconium oxides or activated carbon, or mixtures thereof, which may optionally include other elements. Preferred support materials are, for example, aluminosilicates, zeolites, alumina (Al ₂ O ₃ ) or cerium oxide. More preferably, the support material comprises or consists of cerium oxide.

The porous support material preferably has one or more of the following material properties: i) the average pore diameter is in the range of 1 to 423 nm; ii) the pore volume is in the range of 0.1 to 2 ml/g; and iii) the BET surface area is in the range of 10 to 2050 m 2 /g.

These values are determined by the mercury (Hg) method of DIN 66133 and the nitrogen (N ₂ ) adsorption method of DIN 66131 and DIN 66135. Preferred porous support materials have all of the surface parameters mentioned.

More particularly, the porous support material has one or more of the following material properties: i) an average pore diameter in the range of 8 to 14 nanometers; ii) a pore volume in the range of 0.9 to 1.1 milliliters per gram; iii) a BET surface area of 300 Up to 400 square meters / gram.

In the context of the present invention, an ionic liquid (abbreviated as IL) is understood to mean a liquid which is at a pressure of 101 325 Pa and below 100 ° C, preferably below 50 ° C and more preferably below or equal to The temperature at 25 ° C is in the liquid state and it has virtually no detectable vapor pressure as disclosed in Angew. Chem. Int. Ed. 2000, 39, 3772-3789. They should be distinguished from the inert solvents used to prepare the compositions of the invention. The ionic liquid (IL) used may be any ionic liquid having the above properties. Preferably, the anion is selected from the group consisting of tetrafluoroborate ([BF ₄ ] ^- ), hexafluorophosphate ([PF ₆ ] ^- ), dicyanamide ion ([N(CN) ₂ ) ] ^- ), bis(trifluoromethanesulfonyl)imide ion ([NTf ₂ ] ^- ), tricyanomethylated ([C(CN) ₃ ] ^- ), tetracyanate ([B(CN)) ₄ ] ^- ), halide (Cl ^- , Br ^- , F ^- , I ^- ), hexafluoroantimonate ([SbF ₆ ] ^- ), hexafluoroarsenate ([AsF ₆ ] ^- ), sulfate ([SO ₄ ] ^2- ), tosylate ([C ₇ H ₇ SO ₃ ] ^- ), triflate (CF ₃ SO ₃ ^- ), nonafluorobutanesulfonate ([C ₄ F ₉ SO ₃ -], Pentac(pentafluoroethyl)trifluorophosphate ([PF ₃ (C ₂ F ₅ ) ₃ ]-), thiocyanate ([SCN] ^- ), carbonate ([CO ₃ ] ^2- ), [R ^A -COO] ^- , [R ^A -SO ₃ ] ^- , [R ^A PO ₄ R ^B ] ^- or [(R ^A -SO ₂ ) ₂ N] ^- , wherein R ^A and R ^B are the same or different and each is a linear or branched, aliphatic or alicyclic alkyl or perfluoroalkyl group having 1 to 12 carbon atoms or a C ₅ -C ₁₈ -substituted aryl group, a C ₅ -C ₁₈ -substituted aryl group C ₁ -C ₆ - alkyl or C ₁ -C ₆ - alkyl -C ₅ -C ₁₈ - substituted aryl, each of which may be substituted with a halogen atom; and the cation is selected from As those of the group comprising ionic liquids: general formula _{[NR a R b R c R} d] + of the quaternary ammonium cations, wherein _{R a, R b, R c} , R d is selected from C ₁ -C ₆ - An alkyl group; _a phosphonium cation of the formula [PR _a R _b R _c R _d ] ⁺ wherein R _a , R _b , R _c , R _{d are} selected from C ₁ -C ₆ -alkyl; imidazole of formula (A) Ruthenium cation

Wherein the imidazole ring may be substituted with at least one group R ^na, R ^na group which is selected from C ₁ -C ₈ - alkyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ - alkyl substituted amine, C ₅ -C ₁₂ - aryl group or a substituted C ₅ -C ₁₂ - aryl-substituted -C ₁ -C ₆ - alkyl and where n = 1,2,3 or 4; pyridine of formula (B) of the cation

Wherein the pyridine ring may be substituted with at least one group R ^na, R ^na group which is selected from C ₁ -C ₆ - alkyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ - alkyl substituted amine, C ₅ -C ₁₂ - aryl group or a substituted C ₅ -C ₁₂ - aryl-substituted -C ₁ -C ₆ - alkyl, and wherein n = 1 or 2; pyrazol formula (C) of the azole cation

Wherein the pyrazole ring may be substituted with at least one group R ^na, R ^na group which is selected from C ₁ -C ₆ - alkyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ - alkyl substituted amine, C ₅ -C ₁₂ -substituted aryl or C ₅ -C ₁₂ -substituted aryl-C ₁ -C ₆ -alkyl and wherein n = 1 or 2; triazolium cation of formula (D)

Wherein the triazole ring may be substituted with at least one group R ^na, R ^na group which is selected from C ₁ -C ₆ - alkyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ - alkyl substituted amine, C ₅ -C ₁₂ -substituted aryl or C ₅ -C ₁₂ -substituted aryl-C ₁ -C ₆ -alkyl and wherein n = 1, 2 or 3.

The preferred ionic liquid in the composition of the present invention is an imidazolium structure having the general formula (A) as a cation.

Wherein the imidazole ring may be substituted with at least one group R ^na, R ^na group which is selected from C ₁ -C ₈ - alkyl and where n = 1,2,3 or 4.

More preferably, in the composition of the present invention, the ionic liquid is selected from the group comprising: a) 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine, b) 1 -butyl-3-methylimidazolium hexafluorophosphate, c) 1-butyl-3-methylimidazolium tetrafluoroborate.

Suitable organophosphorus compounds for use in the compositions of the invention are disclosed in DE 10 2011 085 883 A1. Preferably, the composition of the invention comprises an organophosphorus compound having structural element (II):

Wherein W is selected from: - hydrogen; - aliphatic, aromatic, heteroaromatic, fused aromatic, fused aromatic-heteroaromatic hydrocarbon radical, and has any other desired substitution; - P ^III (G ² ) ( G ³ ) base:

Wherein G ² and G ³ are each selected from the group consisting of: hydrogen; linear or branched, aliphatic or aromatic or heteroaromatic or fused aromatic or fused aromatic-heteroaromatic hydrocarbon radicals, and having any other desired substitutions ; F, Cl, Br, I, or -OR ¹⁸ , -C(O)R ¹⁹ , -CO ₂ R ²⁰ , -CO ₂ M ¹ , -SR ²¹ , -SOR ²² , -SO ₂ R ²³ , -SO _{^{3 R 24, -SO 3 M 2}} , -NR 25 R 26; wherein ^{R 18, R 19, R 20} , R 21, R 22, R 23, R 24, R 25, R 26 is selected from: hydrogen, without a substituted or substituted, straight or branched, aliphatic or aromatic hydrocarbon group; -OR ²⁷ ; wherein R ^{27 is} selected from the group consisting of: hydrogen, unsubstituted or substituted, straight or branched chain, aliphatic or aromatic hydrocarbon group; F, Cl, Br, I; wherein M ¹ and M ^{2 are} selected from the group consisting of alkali metal, alkaline earth metal, ammonium, cerium, and wherein the definitions of M ¹ and M ² can be independently selected, wherein G ² and G ^{3 are} defined Independently selected, and G ² and G ³ may be covalently linked to each other, -SiR ²⁸ R ²⁹ R ³⁰ ; wherein R ²⁸ , R ²⁹ , R ³⁰ = hydrogen; linear or branched, aliphatic or aromatic or hetero An aromatic or fused aromatic or fused aromatic-heteroaromatic hydrocarbon group, and having any other desired substitution; wherein R ²⁸ , R ²⁹ The definition of R ³⁰ can be independently selected and wherein R ²⁸ and R ²⁹ can be covalently linked to each other.

Among the compositions of the present invention, other preferred organophosphorus gametes include structural elements (III):

Wherein Z is a G ⁴ or X ¹ -G ¹ -X ² unit, and G ^{4 is} selected from the group consisting of: hydrogen; linear or branched, aliphatic or aromatic or heteroaromatic or fused aromatic or fused aromatic - a heteroaromatic hydrocarbon group, and having any other desired substitution; F, Cl, Br, I, or -OR ³¹ , -C(O)R ³² , -CO ₂ R ³³ , -CO ₂ M ¹ , -SR ³⁴ , -SOR ³⁵ , -SO ₂ R ³⁶ , -SO ₃ R ³⁷ , -SO ₃ M ² , -NR ³⁸ R ³⁹ , wherein R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ^{39 are} selected from the group consisting of: hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon group; -OR ⁴⁰ ; wherein R ^{40 is} selected from: hydrogen, unsubstituted or substituted, straight a chain or branched, aliphatic or aromatic hydrocarbon group; wherein M ¹ and M ^{2 are} selected from the group consisting of alkali metals, alkaline earth metals, ammonium, cerium, and wherein the definitions of M ¹ and M ² are independently selected.

Among the compositions of the present invention, other preferred organophosphorus gametes include structural elements (IV):

Wherein G ⁵ and G ^{6 are} selected from the group consisting of: hydrogen; linear or branched, aliphatic or aromatic or heteroaromatic or fused aromatic or fused aromatic-heteroaromatic hydrocarbon radicals, and having any other desired substitutions; F, Cl, Br, I, or -OR ⁴¹ , -C(O)R ⁴² , -CO ₂ R ⁴³ , -CO ₂ M ¹ , -SR ⁴⁴ , -SOR ⁴⁵ , -SO ₂ R ⁴⁶ , -SO ₃ R ⁴⁷ , -SO ₃ M ² , -NR ⁴⁸ R ⁴⁹ , wherein R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ^{49 are} selected from the group consisting of: hydrogen, unsubstituted Or a substituted, straight or branched, aliphatic or aromatic hydrocarbon group; -OR ⁵⁰ ; wherein R ^{50 is} selected from the group consisting of: hydrogen, unsubstituted or substituted, straight or branched, aliphatic or aromatic hydrocarbon radical; M ¹ and M ^{2 are} selected from the group consisting of alkali metal, alkaline earth metal, ammonium, cerium, and wherein the definitions of M ¹ and M ² can be independently selected, wherein the definitions of G ⁵ and G ⁶ can be independently selected, and G ⁵ and G ⁶ can be covalently connected to each other.

In one embodiment of the invention, W is a P ^III (G ² )(G ³ )- group.

In one embodiment of the invention, G ² , G ³ = -OR ¹⁸ .

In one embodiment of the invention, G ⁵ , G ⁶ = -OR ⁴¹ .

In one embodiment of the invention, X ¹ , X ² =O.

In one embodiment of the invention, G ¹ comprises a di extended aryl group and has any other desired substitutions.

In one embodiment of the invention, G ¹ comprises a structural element (V):

Wherein R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ = hydrogen; straight or branched chain, aliphatic or aromatic or heteroaromatic or fused aromatic or fused An aromatic-heteroaromatic hydrocarbon group, and having any other desired substitution; F, Cl, Br or I, or -OR ⁵⁹ , -COR ⁶⁰ , -CO ₂ R ⁶¹ , -CO ₂ M ¹ , -SR ⁶² , SOR ⁶³ , -SO ₂ R ⁶⁴ , -SO ₃ R ⁶⁵ , -SO ₃ M ² , -NR ⁶⁶ R ⁶⁷ , or N=CR ⁶⁸ R ⁶⁹ ; wherein the definitions of R ⁵¹ to R ⁵⁸ can be independently selected and wherein Two or more of R ⁵¹ to R ⁵⁸ may be covalently linked to each other; wherein R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ^{67 are} selected from: hydrogen, not Substituted or substituted, straight or branched, aliphatic or aromatic hydrocarbon radical; -OR ⁶⁸ ; wherein R ^{68 is} selected from: hydrogen, unsubstituted or substituted, straight or branched, aliphatic or aromatic hydrocarbon radical Wherein M ¹ and M ^{2 are} selected from the group consisting of alkali metal, alkaline earth metal, ammonium, cerium, and wherein the definitions of M ¹ and M ² are independently selected, and wherein a and b are the point of attachment to X ¹ and X ² .

In one embodiment of the invention, G ² and G ³ are covalently linked to each other.

One embodiment of the present invention, G ² -G ³ linkage comprising the structural element (VI):

Wherein R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ = hydrogen; straight or branched chain, aliphatic or aromatic or heteroaromatic or fused aromatic or fused An aromatic-heteroaromatic hydrocarbon group, and having any other desired substitution; F, Cl, Br or I, or -OR ⁷⁷ , -COR ⁷⁸ , -CO ₂ R ⁷⁹ , -CO ₂ M ¹ , -SR ⁸⁰ , - SOR ⁸¹ , -SO ₂ R ⁸² , -SO ₃ R ⁸³ , -SO ₃ M ² , -NR ⁸⁴ R ⁸⁵ , or N=CR ⁸⁶ R ⁸⁷ ; wherein the definitions of R ⁶⁹ to R ⁷⁶ can be independently selected and wherein Two or more of R ⁶⁹ to R ⁷⁶ may be covalently linked to each other; wherein R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ^{85 are} selected from the group consisting of: hydrogen, not Substituted or substituted, straight or branched, aliphatic or aromatic hydrocarbon radical; -OR ⁸⁶ ; wherein R ^{86 is} selected from: hydrogen, unsubstituted or substituted, straight or branched, aliphatic or aromatic hydrocarbon radical Wherein M ¹ and M ^{2 are} selected from the group consisting of alkali metals, alkaline earth metals, ammonium, cerium, and wherein the definitions of M ¹ and M ² are independently selected.

Embodiment, G ⁵ and G ⁶ are covalently linked to each other based one embodiment of the present invention.

In one embodiment of the invention, the linkage G ⁵ -G ⁶ comprises the following structural elements (VII):

Wherein R ⁸⁷ , R ⁸⁸ , R ⁸⁹ , R ⁹⁰ , R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ = hydrogen; straight or branched, aliphatic or aromatic or heteroaromatic or fused aromatic or fused An aromatic-heteroaromatic hydrocarbon group, and having any other desired substitution; F, Cl, Br or I, or -OR ⁹⁵ , -COR ⁹⁶ , -CO ₂ R ⁹⁷ , -CO ₂ M ¹ , -SR ⁹⁸ , - SOR ⁹⁹ , -SO ₂ R ¹⁰⁰ , -SO ₃ R ¹⁰¹ , -SO ₃ M ² , -NR ¹⁰² R ¹⁰³ , or N=CR ¹⁰⁴ R ¹⁰⁵ ; wherein the definitions of R ³¹ to R ³⁸ can be independently selected and wherein Two or more of R ⁸⁶ to R ⁹³ may be covalently linked to each other; wherein R ⁹⁵ , R ⁹⁶ , R ⁹⁷ , R ⁹⁸ , R ⁹⁹ , R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , R ^{103 are} selected from the group consisting of: hydrogen, not Substituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon radical; -OR ¹⁰⁴ ; wherein R ^{104 is} selected from the group consisting of: hydrogen, unsubstituted or substituted, straight or branched, aliphatic or aromatic hydrocarbon radical Wherein M ¹ and M ^{2 are} selected from the group consisting of alkali metals, alkaline earth metals, ammonium, cerium, and wherein the definitions of M ¹ and M ² are independently selected.

In one embodiment of the invention, the P ^III (G ² )(G ³ ) group corresponds to the structural formula of the P ^III (G ⁵ )(G ⁶ ) group.

More particularly, in the compositions of the invention, the organophosphorus compound is selected from the group consisting of:

In the composition of the present invention, it is particularly preferable to use the compound (17)

As an organic phosphorus compound.

Preferably, the compositions of the present invention comprise an organic amine. Preferably, the organic amine used comprises at least one group having a 2,2,6,6-tetramethylpiperidine unit according to formula (E):

More preferably, the organic amine in the composition of the invention is selected from the group consisting of compounds of formula (Ea)-(Eh):

Where n=1 to 20

Where n=1 to 12

Where n=1 to 17

Wherein R = C ₆ - to C ₂₀ -alkyl In the composition of the invention, the metal is preferably selected from the group consisting of cobalt, ruthenium, osmium, iridium, especially ruthenium.

The compositions of the present invention can be prepared by mixing the components in any known manner. Preferably, the compositions of the invention are made according to the process according to the invention as described hereinafter or are obtainable therefrom.

The process according to the invention for the preparation of the composition of the invention comprises the following steps: i) a precursor which initially carries at least one compound of a transition metal of the group VIII of the Periodic Table of the Elements; ii) an inert solvent which causes at least one elemental cycle The compound of the Group VIII transition metal is contacted with at least one organophosphorus compound comprising a structural element of formula (I): Iii) adding at least one porous inert support material to the mixture produced by ii); iv) adding at least one ionic liquid and optionally one or more organic amines; v) removing the inert solvent to obtain a composition.

Wherein, preferably, steps i) to iv) are carried out in any order, and wherein preferably, in step i), at least one of the Group VIII transition metals may be initially loaded in an inert solvent.

The composition of the present invention can be used as a catalytically active composition. Preferably, the composition of the present invention is a catalytically active composition in a hydroformylation process for an unsaturated compound or a mixture thereof.

Therefore, according to the present invention, the hydrogenation of an unsaturated compound is carried out. The method is characterized by the use of the composition of the invention as a catalytically active composition. Preferably, the method for hydroformylating an unsaturated compound according to the present invention uses a fixed bed reactor.

The unsaturated compound is preferably selected from the group consisting of C ₂ -C ₄ olefins and industrial mixtures for the presence of, for example, raffinate stream-raffinate I, II or III in the processes of the petrochemical industry and in further processes, in particular It is ethylene, propylene, butene or a mixture comprising these compounds.

The present invention ultimately provides a heterogeneous reaction mixture comprising: 1) at least one unsaturated compound; 2) a gas mixture comprising carbon monoxide, hydrogen, and 3) an aldehyde and conversion products thereof, and the presence of the composition of the invention.

The following examples are illustrative of the invention by way of example, and the scope of the invention is intended to be

Example:

All of the following preparations were carried out under standard protective Schlenk industrial grade under protective gas. Unless otherwise specified, the solvent is applied to a suitable desiccant prior to use (Purification of Laboratory Chemicals, W. L. F. Armarego (author), Christina Chai (author), Butterworth Heinemann (Elsevier), 6th edition, Oxford 2009).

Chemicals

(Ethylacetone oxime) Dicarbonyl ruthenium (I) - abbreviated as (Rh(acac)(CO) ₂ )- and dichloromethane (HPLC purity) was used directly without further purification. Mesoporous cerium oxide is commercially available from Merck KGaA for column chromatography of tantalum 100 (0.2-0.5 mm). In the production of the catalytically active composition, cerium oxide was calcined at 450 ° C for 24 hours, and then stored under reduced pressure at 200 Pa for another 24 hours. The cerium oxide is then stored under an argon atmosphere. Gametes (17) are made according to DE 10 2011 085 883 A1.

From hydrogen and carbon monoxide with a volume ratio of 1:1 ( Syngas consisting of a mixture of 99.97%). Industrial grade C4 blends have the following composition:

[a] GC area is expressed in % (column: Agilent Technologies, length 50 m, inner diameter 0.32 mm, film thickness 0.5 μm, carrier gas enthalpy; detector: FID, carburetor temperature 473.15 K, split ratio 33.5:1, 氦The constant column flow rate is 91.6 ml ^-1 , the detector temperature is 523.15 K, the heating ramp: the starting temperature is 323.15 K, the maintenance time is 15 minutes, and the temperature is heated to 473.15 K at a speed of 25 K min ^-1 , and the maintenance time is 40 minutes each time. Analysis time total 61 minutes)

Preparation of catalytically active composition

All catalytically active compositions were prepared by argon by the Schlenk method. 99.99%) reached. 0.40 mmol of Rh(CO) ₂ (acac) was dissolved in about 160 ml of dichloromethane and stirred for another 10 minutes. A ten-fold excess (1) (molar gametes/rhodium ratio = 10) was added to the hydrazine precursor solution and stirred for another 10 minutes. An ionic liquid (hereinafter referred to as IL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine (abbreviated as [EMIM][NTf ₂ ]) was added to establish the load The degree α is assumed to be a value of 0.1% by volume or 10% by volume. With regard to the SILP catalyst system, the degree of loading α is understood to mean the ratio of the volume of the ionic liquid IL used under standard conditions in each case to the pore volume of the support material used in each case. Thereafter, a four-fold excess of bis-4(2,2,6,6-tetramethylpiperidyl)sebacate (the molar ratio of the ester/gamete = 4) was added, which was optional. The reaction mixture was stirred for 10 minutes. Next, the required amount of calcined cerium oxide, cerium 100 (mass ratio of ruthenium/support material = 0.2%) was added. The resulting suspension was stirred for 60 minutes. Dichloromethane was then extracted under reduced pressure on a rotary evaporator at 700 kPa and 40 ° C, and the obtained powder was dried under high vacuum (40 Pa) for 24 hours. Prior to the use of the catalytically active composition, it was stored under an argon atmosphere.

Catalytic experiment

All hydroformylation experiments were carried out in a fixed bed reactor. The dried catalyst material is loaded into a tubular reactor and secured to either side with a piece of glass wool. The entire system was purged with argon at room temperature and then pressurized at the reaction pressure (argon). If the pressure is not found to decrease, the reactor in the argon stream is heated to the reaction temperature. After the individual volume flow rate is set, the synthesis gas (carbon monoxide and hydrogen; volume = 1 to 1, 99.97%) passed through the reactor for 4 hours. The synthesis gas is metered in via a mass flow regulator (source: Bronkhorst). The reactant metering of the C4 mixture was achieved via an HPLC pump (source: Knauer). In a mixer filled with glass beads, the reactant gas stream is homogenized and thereafter passed from the top into a tubular reactor comprising a catalyst bed. The reactor consisted of stainless steel (diameter 12 mm, length 390 mm) and had a grid for catalyst material positioning on the outlet side. The temperature in the catalyst bed is possibly recorded by an internal thermocouple. The total pressure in the experimental system was adjusted by an electronic pressure holding valve (source: Samson). On the low pressure side, the product gas stream is separated by the aid of a valve to use only a small portion of the total gas stream to enter a gas chromatograph (source: Agilent, model: 6890). A larger proportion goes directly into the product tank. The product gas stream is injected into the gas chromatograph at regular intervals via a valve. The data was evaluated by Agilent's ChemStation software.

analysis

The product gas composition was analyzed by a line gas chromatograph at the experimental run time. The gas chromatograph was equipped with a dimethylpolyoxane coated column (from Agilent Technologies, length 50 m, inner diameter 0.2 mm, film thickness 0.5 micron) and flame ionization detector (FID). Analysis parameter setting: injector temperature 473.15K, split ratio 33.5:1, constant column flow rate 74 ml ^-1 , detector temperature 523.15K, heating ramp: starting temperature 323.15K, maintenance time 15 minutes, 25K The temperature was heated to 473.15 K at a rate of ^-1 , and the maintenance time was 40 minutes, and the total time of analysis was 61 minutes.

result

The catalytically active composition Rh-(17) exhibited an average of 85% normal/isomerization selectivity (◇) (see Figure 1) and the conversion was 12% (□). The surprising thing about this catalyst system is that despite the lack of stabilizers, the observed lifetime of the catalyst at 120 °C is much longer than that of other SILP catalyst systems containing ionic liquids via the addition of organic amines. The reaction profile of the catalytically active composition Rh-(17) exhibited only a slow decay of the conversion reaction from about 650 hours of experimental run time.

In other experimental series for hydroformylation of industrial grade C4-mixtures, the catalytically active composition based on Rh-(17) is improved by the optional addition of at least one organic amine. Advantageously, commercially available di-4(2,2,6,6-tetramethylpiperidinyl) sebacate is used as the organic amine.

DE 10 2011 085 883 A1 discloses a hindered amine derivative as an organic amine in a homogeneous catalytic hydroformylation reaction, in which a tridentate gamete having a ninhydrin derivative as a substrate and a ruthenium as a metal are used, There is no industrial grade effect on the yield and the positional selectivity to the normal aldehyde.

Surprisingly, it has been found that when the composition according to the invention is used in the hydroformylation process of the invention, the conversion of butene (e.g., technical grade C4-mixture) can be increased more than by random addition of a hindered organic amine. 3 times. In another embodiment of the invention (see Figure 2), the conversion was increased to an average of 36 by adding bis(4,2,6,6-tetramethylpiperidyl) sebacate over about 1300 hours. %; the conversion rate not added is only 12% as shown in Figure 1. The yield of the target product can also be improved in the same order by the optional addition of at least one organic amine, preferably bis-4(2,2,6,6-tetramethylpiperidyl)sebacate. It is especially surprising, since the composition according to the invention contains a lower proportion of ruthenium: as is common in heterogeneously catalyzed reactions, the proportion of catalytically active metal is specifically specified in relation to the quality of the support material. The mass of the ruthenium in each portion of the support material is the same (0.2 wt-%) in the two compositions (with or without stabilizer) according to the invention, but in proportion to the composition of the invention comprising the amine It is about 30% lower. Table 2 reveals that the space-time yield of n-pentanal can be increased to an average value of 139.5 kg ^-3 hr ^-1 compared to the value of only 52.2 kg metric ^-3 hr ^-1 which is not optionally added. The space time yield (STY) is calculated as the ratio of the mass flow of the formed aldehyde to the total volume of the composition according to the invention. Especially in large scale continuous operation methods, high space time yields are desirable. Compared to compositions having lower space time yields, compositions of the invention having a high space time yield are equivalent to higher manufacturing rates, i.e., due to reduced catalyst volume and cost, the reaction vessel is relatively small in size and thus preferred. Heat dissipation and additionally lower lower capital.

It is noted that, in addition to high yield and high normal selectivity, the homogeneous hydrogen methylation process is carried out by applying a tridentate ligninol-based gamete as disclosed in DE 10 2011 085 883 A1. Improve resistance, examples Features such as water resistance cannot be converted to heterogeneous hydrogen formazanization by, for example, application of a composition of the invention using gametes (17), which can be achieved by lower normal selectivity values (Figure 1). This is evident in comparison with the one obtained by the homogeneous hydroformylation method.

SUMMARY OF THE INVENTION The present invention provides a method for carrying out a hydroformylation reaction in the hydroformylation process of the present invention in a long-term stable manner using a composition according to the present invention. The composition of the present invention is a three-toothed, scorpion-based gamete. For the bottom, at least one organic amine is added by random. The reaction time is considered to have long-term stability in the context of the present invention in the range of about 900 to 2200 hours. Even in the light of the knowledge of DE 10 2011 085 883 A1, unexpectedly, in contrast to the homogeneous hydroformylation reaction, in the SILP-catalyst system of heterogeneous hydroformylation, at least one organic is optionally added. The amines have a positive effect on the conversion rate and yield of the reaction parameters as well as the space time yield (parameters important for industrial availability). The results presented in Table 2 show that the hydroformylation of the technical grade C4 mixture is increased by a factor of 2.7 compared to the composition of the SILP catalyst system not added accordingly. In other advantages, the use of the composition according to the invention in the hydroformylation process of the invention results in a significant reduction in the demand for precious metal ruthenium compared to the process steps in which at least one organic amine is not optionally added.

Claims (15)

A composition comprising a) at least one support material, preferably porous; b) at least one ionic liquid; c) at least one metal selected from the transition group of Group VIII of the Periodic Table of Elements; d) at least one comprising Organic phosphorus compounds of structural elements of formula (I): Wherein the compound comprises at least two OP ^III bonds, which may be derived from the same P ^III or from different P ^III ; wherein, if structural element (I) is present twice in the compound, they are each via C10-C10 'Carbon bond or via the following X ¹ -G ¹ -X ² unit: -X ¹ -G ¹ -X ² - wherein X ^{1 is} bonded to P ^III in the first structural element (I) and the X ² bond To P ^III in the second structural element (I), and G ¹ = linear or branched, aliphatic or aromatic or heteroaromatic or fused aromatic or fused aromatic-heteroaromatic hydrocarbon, and Any other substitution desired; wherein X ¹ , X ^{2 are} selected from: O, NY ¹ , CY ² Y ³ ; wherein the definitions of X ¹ and X ² are independently selected; wherein Y ¹ , Y ² , Y ^{3 are} selected from: a hydrogen, unsubstituted or substituted aliphatic or unsubstituted or substituted aromatic hydrocarbon group; wherein the definitions of Y ¹ to Y ³ may be independently selected; wherein two or more of Y ¹ to Y ³ may be mutually Covalently linked; wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ^{7 are} selected from: hydrogen, unsubstituted or substituted, straight or branched, aliphatic or aromatic hydrocarbon radical ;F, Cl, Br, I, -OR ⁸ , -C(O)R ⁹ , -CO ₂ R ^{1 0} , -CO ₂ M ¹ , -SR ¹¹ , -SOR ¹² , -SO ₂ R ¹³ , -SO ₃ R ¹⁴ , -SO ₃ M ² , -NR ¹⁵ R ¹⁶ ; wherein R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ^{16 are} selected from the group consisting of: hydrogen, unsubstituted or substituted, straight or branched, aliphatic or aromatic or heteroaromatic or fused aromatic or a fused aromatic-heteroaromatic hydrocarbon group; -OR ¹⁷ ; wherein R ^{17 is} selected from the group consisting of: hydrogen, unsubstituted or substituted, straight or branched chain, aliphatic or aromatic hydrocarbon group; wherein R ¹ to R ^{17 are} two Or a plurality of which may be covalently linked to each other; wherein M ¹ and M ^{2 are} selected from the group consisting of alkali metal, alkaline earth metal, ammonium, cerium, and wherein the definitions of M ¹ and M ² are independently selected; e) optionally one or more Organic amines. The composition of claim 1, wherein the ionic liquid is selected from the group consisting of: a) 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) ruthenium; b) 1-butyl-3-methylimidazolium hexafluorophosphate; c) 1-butyl-3-methylimidazolium tetrafluoroborate. The composition of claim 1, wherein the organic amine comprises at least one 2,2,6,6-tetramethylpiperidine unit as a structural element. The composition according to claim 1, wherein the porous support material has the following material properties: i) an average pore diameter in the range of 1 to 423 nm; and ii) a pore volume in the range of 0.1 to 2 ml/g. ; iii) The BET surface area is in the range of 10 to 2050 m 2 /g. The composition according to claim 1, wherein the support material comprises or consists of an oxide of cerium, an oxide of aluminum, an oxide of titanium or an oxide of zirconium or activated carbon. The composition of claim 1, wherein the metal is selected from the group consisting of cobalt, ruthenium, osmium, and iridium. A composition according to item 6 of the patent application, wherein the metal is ruthenium. The composition according to claim 1, wherein the compound of the formula (17) is selected as the organophosphorus compound: A method of preparing a composition according to the first aspect of the patent application, comprising the steps of: i) initially loading at least one compound of a transition metal of Group VIII of the Periodic Table of the Elements; ii) using at least one element of an inert solvent The compound of the transition metal of Group VIII of the Periodic Table is contacted with at least one organophosphorus compound comprising a structural element of formula (I): Iii) adding at least one porous inert support material to the mixture produced by ii); iv) adding at least one ionic liquid and optionally one or more organic amines; v) removing the inert solvent to obtain a composition. A use of a composition according to claim 1 of the patent application as a catalytically active composition in a process for the hydroformylation of an unsaturated compound. A method for hydroformylating an unsaturated compound, which is characterized in that a composition according to item 1 of the patent application is used as a catalytically active composition. According to the method of claim 11, the fixed bed reactor containing the composition according to the first aspect of the patent application is used. The method of claim 11, wherein the unsaturated compound is selected from the group consisting of C ₂ -C ₄ olefins and industrial mixtures thereof. The method of claim 13, wherein the unsaturated compound is selected from the group consisting of ethylene, propylene, butylene, and industrial mixtures thereof. A heterogeneous reaction mixture comprising: 1.) at least one unsaturated compound; 2.) a gas mixture comprising carbon monoxide, hydrogen, and 3.) an aldehyde and a conversion product thereof, wherein the composition of claim 1 is present.