WO2016155337A1

WO2016155337A1 - Internal olefin hydroformylation process for producing high normal/iso ratio aldehydes

Info

Publication number: WO2016155337A1
Application number: PCT/CN2015/095595
Authority: WO
Inventors: 丁云杰; 李存耀; 严丽
Original assignee: 中国科学院大连化学物理研究所
Priority date: 2015-04-03
Filing date: 2015-11-26
Publication date: 2016-10-06
Also published as: CN106140303B; CN106140303A

Abstract

Disclosed is an internal olefin hydroformylation process for producing high normal/iso ratio aldehydes that utilizes a multiphase catalyst having one, two, or three of the metals Rh, Co, and Ir as active components, and a phosphine-containing organic hybrid polymer with a multilevel porous structure as a carrier, wherein the phosphine-containing organic hybrid polymer is copolymerized from an olefin group-containing polydentate organophosphine ligand and a monodentate organophosphine ligand. Such a ligand-based multiphase catalyst is suitable for use in reactors such as a fixed bed, a slurry bed, a bubble bed, or a trickle bed. The multiphase catalyst provided in the present invention has a favorable performance in an internal olefin hydroformylation reaction, and under the action of such a catalyst, an internal olefin is first isomerized into a terminal olefin and then hydroformylated to selectively produce a corresponding normal aldehyde, resulting in a product aldehyde having a high normal/iso ratio, greater than 15, and the resultant product has an alkane content lower than 1%.

Description

Method for preparing high ortho-isomeric aldehyde by hydroformylation of internal olefin

Technical field

The invention belongs to the field of heterogeneous catalysis and fine chemical industry, and particularly relates to a phosphine-containing organic mixed polymer-metal heterogeneous catalyst, a preparation method thereof and the application thereof for the production of a high ortho-normal aldehyde by hydroformylation of an internal olefin.

Background technique

Hydroformylation of olefins (also known as OXO-Synthesis) refers to the reaction of olefins and synthesis gas (CO/H ₂ ) catalyzed by transition metal carbonyl complexes to form one carbon aldehyde higher than the starting olefins. A homogeneous complexation catalytic process for industrial production. The continuous development of olefin hydroformylation reaction is mainly driven by the petrochemical industry. The petroleum cracking process and the Fischer-Tropsch synthesis process produce a large amount of olefins, which provide cheap synthetic raw materials for hydroformylation and industrialization. The material base; at the same time, the product aldehyde of the olefin hydroformylation reaction is a very useful chemical intermediate, which can be used to synthesize carboxylic acid and corresponding esters, as well as fatty amines. The most important use is that it can be hydrogenated into Alcohols, alcohols themselves can be widely used in the field of fine chemicals as organic solvents, plasticizers and surfactants.

Patent CN1319580A describes a plurality of bidentate phosphite ligands with large steric hindrance, which are hydroformylated with higher olefins of a coordinated homogeneous catalyst such as Rh and Co. The selectivity of the ratio. However, homogeneous catalysts are difficult to recover and ligand synthesis is difficult.

Patent CN1210514A reports a Rh complex catalyst for the hydroformylation of olefins. The Rh complex is a ligand with a multidentate organic nitrogen compound containing at least one tertiary nitrogen group which can be protonated in a weak acid. However, the catalyst is also facing the problem of being difficult to recycle.

In the patent CN102911021A, a composite catalyst system composed of a Rh complex with a biphenyl skeleton or a binaphthyl skeleton bisphosphine ligand, and a triphenylphosphine or a phosphite triphenyl ester monophosphine ligand is used as a catalyst in a linear olefin hydrogen. The normal aldehyde in the formylation reaction has a higher selectivity, which reduces the amount of the expensive bisphosphine ligand, but the catalytic system is homogeneous and the catalyst cannot be reused.

In the patent CN1986055A, the bisphosphite and triphenylphosphine are also combined with Rh to form a composite catalytic system. In the hydroformylation reaction of propylene, the molar ratio of n-butyraldehyde to isobutyraldehyde is more than 20, which significantly prolongs the double sub- The service life of the phosphate ligand significantly reduces the amount of triarylphosphine, but it is also a homogeneous reaction in nature, and it also faces the problem of difficulty in recycling the catalyst.

In 2001, Holger Klein et al. (Angew. Chem. Int. Ed. 2001, 40, No. 18) synthesized a homogeneous ligand of the NAPHOS type, which complexes with Rh after hydrogenation at the terminal olefin and internal olefin Good selectivity was achieved in the formylation reaction (the product aldehyde has a high aspect ratio). However, the catalytic system is essentially a homogeneous reaction, the recovery of the catalyst is difficult, and the cost of the high-carbon olefin including the internal olefin hydroformylation reaction is high.

Billig et al. of UCC Corporation (Joint Carbide Corporation) synthesized biphephos ligands, which have excellent performance in the hydroformylation of propylene. Arno Behr and Christian Vogl et al. further systematically studied the formulation using biphephos ligands. The complex with Rh to catalyze the hydroformyl reaction of internal olefins and terminal olefins (Journal of Molecular Catalysis A: Chemical, 2003, 206, 179-184; 2005, 232, 41-44; 2005, 226, 215-219), product aldehyde Stereoselectivity is good, and Arno Behr and Christian Vogl have done some research on the two-phase olefin hydroformylation. However, the problem of heterogeneous homogeneous catalysts has not been fundamentally solved, the catalyst deactivation is fast, and the recycling of the catalyst is not achieved.

The hydroformylation of internal olefins has been a difficult and hot topic in research. Chemists have devoted a lot of efforts to the synthesis of homogeneous multidentate ligands for the internal olefin hydroformylation reaction, but there is no specific Heterogeneous catalysts and processes for the hydroformylation of internal olefins have emerged.

Summary of the invention

In order to solve the above problems, it is an object of the present invention to provide a phosphine-containing organic polymer-metal heterogeneous catalyst and its use in the hydroformylation of an internal olefin to produce a high ortho-ratio aldehyde.

The technical solution of the present invention is:

A phosphine-containing organic polymer-metal heterogeneous catalyst, one, two or three kinds of metals Rh, Co or Ir as active components, a phosphine-containing organic mixture as a carrier, and a metal catalyst in a catalyst The loading is from 0.01 to 10% by weight (preferably from 0.1 to 5% by weight, more preferably from 0.1 to 2% by weight), and the phosphine-containing organic polymer mixture is composed of a polydentate organophosphine ligand containing an olefin group and a monodentate organophosphine group containing an olefin group. Bulk copolymerization (a typical vinyl-containing monophosphine diphosphine ligand synthesis method is described in the literature Chem. Commun., 2014, 50, 11844 and J. Am. Chem. Soc., 2015, 137, 5204), activity The metal component forms a multiple coordination bond with the exposed P in the carrier carrier, and the formed catalyst excels in the process of hydroformylation of the internal olefin to produce a high orthorhombic aldehyde.

The olefin group is preferably a vinyl group, and the olefin group-containing polydentate organophosphine ligand is a vinyl group-containing bidentate phosphite organophosphorus ligand, and the olefin group-containing monodentate organophosphine compound The body is a vinyl-containing triphenylphosphine ligand.

The organic hybrid carrier has a multi-stage pore structure, a specific surface area of 100-3000 m ² /g, and contains macropores, mesopores and micropores (wherein macropores account for 5-50% of the total pore volume, mesopores) 5-50% of the total pore volume, micropores account for 5-50% of the total pore volume), pore volume is 0.1-5.0 cm ³ /g, pore size distribution is 0.2-50.0 nm.

The heterogeneous catalyst is a mixture of a polydentate organophosphine ligand and a monodentate organophosphine ligand, and a solvothermal polymerization method is used to initiate polymerization of an olefin group in the organophosphine ligand by a radical initiator to form The multi-stage pore structure contains a phosphine organic mixed polymer as a carrier, the precursor of the active component and the carrier are stirred in an organic solvent, and the active component forms a multi-coordination bond with the exposed P in the phosphine-containing organic polymer carrier, and is evaporated. After the volatile solvent, a heterogeneous catalyst of the coordination bond type is obtained.

The preparation method of the heterogeneous catalyst is:

a) adding a monodentate organophosphine ligand and a polydentate organophosphine ligand, with or without cross-linking, in an organic solvent at 273 to 473 K (preferably 273 to 353 K, more preferably 280 to 300 K) under an inert gas atmosphere And adding a free radical initiator, after mixing, the mixture is stirred for 0.1 to 100 hours, and the preferred stirring time is in the range of 0.1 to 50 hours;

b) Transfer the mixed solution prepared in the step a) to a synthetic autoclave at 273 to 473 K (preferably 323 to 423 K, more preferably 353 to 403 K), and let it stand for 1 to 100 hours by a solvothermal polymerization method under an inert gas atmosphere. (preferably 1 to 50 hours, more preferably 10 to 30 hours) to carry out a polymerization reaction to obtain a phosphine-containing organic mixed polymer;

c) the mixed polymer obtained in the step b) is vacuum-extracted at room temperature to obtain an organic complex containing bare P having a multi-stage pore structure, that is, a support of the heterogeneous catalyst;

d) at 273 to 473 K (preferably 273 to 353 K, more preferably 280 to 300 K), in an inert gas atmosphere, the organic hybrid carrier obtained in the step c) is added to the solvent containing the active component precursor, and stirred at 0.1 to ～ For 100 hours, the stirring time is preferably in the range of 0.1 to 50 hours, after which the organic solvent is removed by vacuum to obtain a heterogeneous catalyst.

The organic solvent described in the step a) is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform; the crosslinking agent is styrene, ethylene, propylene, two One or more of vinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3,5-triethynylbenzene; the free radical initiator is cyclohexanone peroxide One or two or more kinds of dibenzoyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptanenitrile.

The molar ratio of the monodentate organophosphine ligand to the polydentate organophosphine ligand described in step a) is from 0.01:1 to 100:1 (preferably from 0.1:1 to 10:1, more preferably from 1:1 to 10:1) In the case of addition of a crosslinking agent, the molar ratio of the monodentate organophosphine ligand to the crosslinking agent is from 0.01:1 to 10:1 (preferably from 0.1:1 to 10:1, more preferably from 1:1 to 10: 1) The molar ratio of the monodentate organophosphine ligand to the free radical initiator is from 300:1 to 10:1 (preferably from 100:1 to 10:1, more preferably from 100:1 to 20:1), and polymerization is carried out into an organic mixture. The concentration of the monodentate organophosphine ligand in the organic solvent before the polymer is in the range of 0.01 to 1000 g/L (preferably 0.1 to 100 g/L, more preferably 1 to 100 g/L).

The solvent described in the step d) is one or more of water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform, and the active component is Rh, Co, Ir One, two or three, wherein the precursor of Rh is Rh(CH ₃ COO) ₂ , RhH(CO)(PPh ₃ ) ₃ , Rh(CO) ₂₍ acac), RhCl ₃ ; Co(CH ₃ COO) ₂ , Co(CO) ₂ (acac), Co(acac) ₂ , CoCl ₂ ; The precursor of Ir is Ir(CO) ₃ (acac), Ir(CH ₃ COO) ₃ , Ir ( Acac) ₃ , IrCl ₄ . The metal loading in the catalyst ranges from 0.01 to 10% by weight (preferably from 0.1 to 5% by weight, more preferably from 0.1 to 2% by weight).

The prepared P-containing organic hybrid carrier-supporting active metal catalyst is used in the internal olefin hydroformylation reaction, has high catalytic activity and good product selectivity, and can be used for fixed bed, slurry bed, bubbling bed and trickle flow. Bed reaction process. The reaction temperature is 323 to 573 K, the reaction pressure is 0.1 to 10.0 MPa, the gas space velocity is 100 to 20000 h ^-1 , and the liquid hourly space velocity is 0.01 to 10.0 h ^-1 . The main component of the reaction raw material synthesis gas is H ₂ and CO, and further contains one or more of N ₂ , He, CO ₂ and Ar, and the volume content of (H ₂ +CO) is 20 to 100%, H _{2 .} The /CO volume ratio is from 0.5 to 5.0. The raw material internal olefins are mainly derived from C ₄ to C ₂₀ olefins in the process of petroleum catalytic cracking, Fischer-Tropsch synthesis, refinery dry gas recovery, etc. The double bonds may be located at positions 2 to 10 of the carbon chain, and also contain C4 to C20. One or more of alkane. The process and method have strong adaptability, and can be one of C ₄ - C ₂₀ internal olefins (including terminal olefins) or several kinds, the purity of the raw materials is 20-100%, and the product is mainly one carbon atom than the raw material olefin. Normal aldehyde.

The reaction principle of the invention:

The present invention introduces a typical bisphosphine ligand such as an aromatic ring of biphephos into a vinyl (Vinyl) group, that is, a vinyl-containing polydentate organophosphine ligand (Vinyl Biphephos) as a polymerization monomer in an autoclave. Copolymerization with a monodentate organophosphine ligand such as tris(4-vinylphenyl)phosphine to form an organic hybrid having a high surface area and a multi-stage pore structure by solvothermal polymerization, due to the large amount of the organic polymer backbone Exposure of P containing orphaned electrons can form a multi-coordination bond with the active transition metal ion orbit as a catalyst carrier, thereby forming a catalytic active site. In the catalyst, the organophosphine mixed polymer has both the dual functions of a carrier and a ligand, and the active metal component is highly dispersed in the carrier to form a multi-coordination bond with the high concentration of the exposed P. The active metal component is highly dispersed in the monoatomic form in the organophosphine polymer carrier, which greatly improves the utilization efficiency of the metal. Moreover, the active component is not easily lost, the catalyst has a long service life, and the multidentate phosphine ligand in the skeleton has a remarkable steric effect, and the prepared catalyst can significantly improve the stereoselectivity of the product.

The catalyst organic hybrid carrier skeleton provided by the invention contains P, and the organic mixture has the dual functions of the ligand and the carrier; the active metal component can be dispersed in such a large surface area in a single atom or ion manner. In the pore structure organic mixed polymer carrier, the metal utilization efficiency is greatly improved. The monophosphine ligand structural unit in the carrier organophosphine mixed polymer skeleton makes the mixed polymer have a higher P concentration, and easily forms a double or multiple metal-P coordination bond with the active metal component, and the coordination bond has a strong bond. The chemical bonding ability makes the active component not easily lost.

The beneficial effects of the invention are:

The heterogeneous catalyst framework of the present invention contains a multidentate and monodentate organophosphine ligand structural unit, wherein the monodentate organophosphine ligand has a relatively high P on the surface of the mixed polymer, and the polydentate phosphine ligand is With significant steric effect, the active metal atom or ion forms a multi-coordination bond with the exposed P on the mixed polymer, the active component is not easily lost, and the active component of the catalyst is Rh, Co or Ir. Stereoselective, the mixed polymer has a high specific surface area multi-stage pore structure, and has the dual functions of a carrier and a ligand. The active metal component may be highly dispersed in the monoatomic form in the pore or surface of the organic phosphine polymer carrier, thereby improving The utilization efficiency of the metal component.

The coordination-type heterogeneous catalyst is suitable for a reaction process such as a fixed bed, a slurry bed, a bubbling bed and a trickle bed, and the process and method for producing the corresponding aldehyde by hydroformylation of the internal olefin provided by the present invention can be used. In a reaction process such as a fixed bed, a slurry bed, a bubbling bed and a trickle bed, the internal olefin is first isomerized to a terminal olefin in a hydroformylation reaction, thereby selectively producing a higher value normal aldehyde. It solves the problems of long-term reactivity and selectivity in the process of multi-phase formation of internal olefin hydroformylation, and serious loss of metal components.

The heterogeneous catalyst provided by the invention has a good performance in the internal olefin hydroformylation reaction, and the internal olefin is in this class. Under the action of the catalyst, the isomerization to the terminal olefin is first carried out, and the hydroformylation reaction is further carried out to selectively form the corresponding normal aldehyde. Therefore, the product aldehyde has a high aspect ratio and can be higher than 15, and the obtained product has an alkane content. Below 1%, the heterogeneous catalyst has good stability, and the separation of the catalyst from the reactants and products is simple and efficient. The production cost of normal aldehyde is greatly reduced, and a new industrialization technology is provided for the hydroformylation reaction of internal olefins.

DRAWINGS

In Figure 1, Figure A shows a typical olefin-based functionalized bisphosphine ligand, and Figure B shows a schematic diagram of Vinyl Biphephos.

Figure 2 is a schematic diagram of the Vinyl Biphephos polymerization technology route.

Figure 3 is a schematic diagram of a typical monodentate organophosphine ligand and a multidentate organophosphine ligand and a crosslinking agent used in the polymerization, wherein L1-L16 is a monodentate organophosphine ligand, and L17-L19 is a multidentate organic Phosphine ligands, L20 and L21 are crosslinkers.

Figure 4 is a ¹ H spectrum of Vinyl Biphephos ligand.

Figure 5 shows the ¹³ C spectrum of the Vinyl Biphephos ligand.

Figure 6 is a ³¹ P spectrum of Vinyl Biphephos ligand.

Figure 7 is a high resolution mass spectrum of Vinyl Biphephos ligand.

Figure 8 is a graph showing the thermogravimetric curve of the catalyst synthesized in Example 1 under a N ₂ atmosphere.

detailed description

The following examples are intended to better illustrate the invention but are not intended to limit the scope of the invention.

The typical monophosphine ligand tris(4-vinylphenyl)phosphine (L1) is synthesized by adding magnesium powder to a 500 ml three-neck round bottom flask with magnetic stirrer in an ice water bath and a nitrogen atmosphere. g, a mixed solution of p-bromostyrene and anhydrous diethyl ether (18.3 g of p-bromostyrene + 100 ml of anhydrous diethyl ether) was added dropwise, and the resulting reaction mixture was stirred at room temperature for 2 hours to complete the reaction. A mixed solution of phosphorus trichloride and anhydrous diethyl ether (4.6 g of phosphorus trichloride + 10 ml of anhydrous diethyl ether) was added dropwise under ice water, and the obtained mixture was stirred at room temperature for 2 hr. 50 ml of deionized water was added to the reaction system under ice-water bath, and the mixture was reacted at room temperature for 2 hours. The organic product obtained by liquid separation and the organic phase is evaporated to remove the solvent, and purified by silica gel column chromatography, using silica gel as a stationary phase and ethyl acetate/petroleum ether (volume ratio 1:10) as a mixed solvent. The eluent is finally obtained as a white powdery solid, which is tris(4-vinylphenyl)phosphine (L1).

The typical bisphosphine ligand Vinyl Biphephos (Fig. 1) is synthesized according to the literature (Org. Lett., 2009, 11, 971).

And B:

In an ice water bath and a nitrogen atmosphere, 7.6 g of A, 50 mg of DMAP (4-dimethylaminopyridine) and 32 mg of acetic anhydride were sequentially added to a 500 ml three-necked flask, and after fully reacting, it was purified by a silica gel column to obtain C:

C and

The reaction is purified by silica gel column to obtain D:

Reducing D with LiH ₄ Al in the presence of KOH in an ethanol solution yields E:

In a 500 ml three-necked flask, 100 ml of toluene, 10 ml of triethylamine, and then 3.5 g of E and 5.0 g of B were added in an ice water bath under a nitrogen atmosphere, and the reaction was sufficiently stirred at room temperature for 2 h. Using silica gel as the stationary phase and a mixed solvent of ethyl acetate/petroleum ether (1:10 by volume) as an eluent, a gray powdery solid was obtained, which was Vinyl Biphephos.

Example 1

In 298 K and an inert gas atmosphere, 10.0 g of Vinyl Biphephos monomer (Fig. 1) was dissolved in 100.0 ml of tetrahydrofuran solvent while 2.5 g of comonomer tris(4-vinylphenyl)phosphine (L1) was added. To the above solution, 1.0 g of a radical initiator azobisisobutyronitrile was added and stirred for 2 hours. The stirred solution was transferred to an autoclave and polymerized by solvothermal polymerization at 373 K under an inert gas atmosphere for 24 h. The solution after the above polymerization was cooled to room temperature, and the solvent was evacuated under vacuum at room temperature to obtain an organic phosphine mixed polymer copolymer copolymerized with Vinyl Biphephos and tris(4-vinylphenyl)phosphine organic monomer. Figure 2 is a schematic diagram of the technical route of Vinyl Biphephos organic hybrid carrier polymerization. Figure. 3.13 mg of acetylacetone tricarbonyl hydrazine was weighed and dissolved in 10.0 ml of tetrahydrofuran solvent, and 1.0 g of an organic polymer carrier obtained by copolymerization of Vinyl Biphephos and tris(4-vinylphenyl)phosphine was added, and the mixture was inert at 298 K. The catalyst was stirred under a gas atmosphere for 24 hours, and then the solvent was evacuated under a room temperature to obtain an excellent catalyst for the hydroformylation reaction of the internal olefin.

Example 2

In Example 2, except that 10.0 g of the comonomer tris(4-vinylphenyl)phosphine (L1) was weighed, instead of 2.5 g of the comonomer tris(4-vinylphenyl)phosphine (L1), the rest The catalyst synthesis process was the same as in Example 1.

Example 3

In Example 3, the synthesis process of the remaining catalyst was the same as in Example 1 except that 0.1 g of a radical initiator azobisisobutyronitrile was weighed instead of 1.0 g of a radical initiator azobisisobutyronitrile.

Example 4

In Example 4, the catalyst synthesis procedure was the same as in Example 1 except that 50.0 ml of tetrahydrofuran solvent was used instead of 100.0 ml of tetrahydrofuran solvent.

Example 5

In Example 5, the catalyst synthesis process was the same as in Example 1 except that 100.0 ml of a dichloromethane solvent was used instead of 100.0 ml of a tetrahydrofuran solvent.

Example 6

In Example 6, the catalyst synthesis process was the same as in Example 1 except that the 393 K polymerization temperature was used instead of the 373 K polymerization temperature.

Example 7

In Example 7, the catalyst synthesis process was the same as in Example 1 except that the polymerization time of 12 h was used instead of the polymerization time of 24 h.

Example 8

In Example 8, the catalyst synthesis process was the same as in Example 1 except that 10.0 g of L20 was further added as a crosslinking agent.

Example 9

In Example 9, the catalyst synthesis process was the same as in Example 1 except that 1.0 g of styrene was further added as a crosslinking agent.

Example 10

In Example 10, 14.05 mg of acetylacetone dicarbonyl cobalt was added in place of acetylacetone tricarbonyl hydrazine in 10.0 ml of tetrahydrofuran solvent, and the rest of the catalyst synthesis process was the same as in Example 1.

Example 11

In Example 11, 2.05 mg of acetylacetone tricarbonyl hydrazine was weighed in place of acetylacetone tricarbonyl hydrazine in 10.0 ml of tetrahydrofuran solvent, and the rest of the catalyst synthesis process was the same as in Example 1.

Example 12

The catalyst prepared above was placed in a fixed bed reactor of 0.5 g, and both ends were charged with quartz sand. The micro feed pump pumps 2-octene at a flow rate of 0.1 ml/min. The mass flow meter controls the synthesis gas (volume ratio H ₂ :CO=1:1) with a space velocity of 1000 h ^-1 at 373 K and 1 MPa. Hydroformylation reaction. The reaction was collected in an ice bath cooled collection tank. The obtained liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector using n-propanol as an internal standard. The tail gas from the collection tank was analyzed online using an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 1.

Example 13

The catalyst prepared in Examples 1-11 was placed in a 0.5 g fixed bed reactor, and both ends were charged with quartz sand. The micro feed pump is pumped into cis-4-hexene at a flow rate of 0.1 ml/min. The mass flow meter controls the synthesis gas (volume ratio H ₂ :CO=1:1) at a space velocity of 1000 h ^-1 at 373 K and 1 MPa. The hydroformylation reaction is carried out. The reaction was collected in an ice bath cooled collection tank. The obtained liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector using n-propanol as an internal standard. The tail gas from the collection tank was analyzed online using an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 2.

Table 1 Specific surface area and 2-octene reaction data of the catalysts synthesized in Examples 1-13

*Experimental conditions are 100 ° C, 1 MPa, 2-octene flow rate is 0.1 ml / min, synthesis gas (CO: H ₂ = 1:1) space velocity 1000 h ^-1 , all metals are considered active sites in TOF calculation . ** indicates a reaction temperature of 230 °C. The active component of Example 10 was Co, and the active component of Example 11 was Ir.

Table 2 Specific surface area of catalyst synthesized in Examples 1-13 and cis-4-hexene reaction data

*Experimental conditions are 100 ° C, 1 MPa, cis-4-hexene flow rate is 0.1 ml / min, synthesis gas (CO: H ₂ = 1:1) space velocity 1000 h ^-1 , all metals are considered active in TOF calculation Site. ** indicates a reaction temperature of 230 °C. The active component of Example 10 was Co, and the active component of Example 11 was Ir.

Claims

A process for the hydroformylation of internal olefins to produce a high n-isomeric aldehyde, characterized in that the reaction is carried out in the presence of a phosphine-containing organic polymer-metal heterogeneous catalyst in which the metal Rh, Co or One, two, three of Ir as active components, a phosphine-containing organic mixture as a carrier, and a phosphine-containing organic mixture from a polydentate organophosphine ligand containing an olefin group and a single tooth containing an olefin group The organic phosphine ligand is copolymerized, and the metal loading in the catalyst ranges from 0.01 to 10% by weight.
The method of claim 1 wherein said olefinic group is a vinyl functional group.
The method of claim 1 wherein said olefin-containing polydentate organophosphine ligand is a vinyl-containing bidentate phosphite organophosphorus ligand, said olefin-containing monodentate The organophosphine ligand is a triphenylphosphine ligand containing a vinyl group.
The method according to claim 1, wherein said organic hybrid carrier has a multi-stage pore structure, a specific surface area of 100 to 3000 m 2 /g, a pore volume of 0.1 to 5.0 cm 3 /g, and a pore size distribution. It is 0.2 to 50.0 nm.
The method according to claim 1, wherein the heterogeneous catalyst is a mixture of a polydentate organophosphine ligand and a monodentate organophosphine ligand, and a solvothermal polymerization method is used to initiate the organic reaction via a free radical initiator. The olefin group in the phosphine ligand is polymerized to form a phosphine-containing organic mixture having a multi-stage pore structure as a carrier, and the precursor of the active component and the carrier are stirred in an organic solvent, and the active component and the phosphine-containing organic mixture are mixed. The exposed P in the carrier forms a multiple coordinate bond, and after evaporation of the volatile solvent, a heterogeneous catalyst of a coordination bond type is obtained.
The method of claim 5 wherein:

a) adding a monodentate organophosphine ligand and a polydentate organophosphine ligand in an organic solvent at 273 to 473 K under an inert gas atmosphere, with or without a crosslinking agent, and then adding a free radical initiator, after mixing, The mixture is stirred for 0.1 to 100 hours, and the preferred stirring time is in the range of 0.1 to 50 hours;

b) transferring the mixed solution prepared in the step a) to a synthetic autoclave, 273 to 473 K, under an inert gas atmosphere, using a solvothermal polymerization method, and allowing to stand for 1 to 100 hours for polymerization to obtain a phosphine-containing organic compound. Polymer

c) the mixed polymer obtained in the step b) is vacuum-extracted at room temperature to obtain an organic complex containing bare P having a multi-stage pore structure, that is, a support of the heterogeneous catalyst;

d) adding the organic polymer carrier obtained in the step c) to a solvent containing the precursor of the active component in an inert gas atmosphere at 273 to 473 K, and stirring for 0.1 to 100 hours, preferably for a period of 0.1 to 50 hours. Thereafter, the organic solvent was removed by vacuum to obtain a heterogeneous catalyst.
The method according to claim 6, wherein the organic solvent in the step a) is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform; The crosslinking agent is one or more of styrene, ethylene, propylene, divinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3,5-triethynylbenzene; The radical initiator is one or more of cyclohexanone peroxide, dibenzoyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptanenitrile;

The solvent described in the step d) is one or more of water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform, and the active component is Rh, Co, Ir One or more of them, wherein the precursor of Rh is Rh(CH 3 COO) 2 , RhH(CO)(PPh 3 ) 3 , Rh(CO) 2 (acac), RhCl 3 ; the precursor of Co is Co ( CH 3 COO) 2 , Co(CO) 2 (acac), Co(acac) 2 , CoCl 2 ; The precursor of Ir is Ir(CO) 3 (acac), Ir(CH 3 COO) 3 , Ir(acac) 3 , IrCl 4 , the metal loading in the catalyst ranges from 0.01 to 10 wt%.
The method according to claim 6, wherein the molar ratio of the monodentate organophosphine ligand to the polydentate organophosphine ligand in step a) is from 0.01:1 to 100:1, and is added to the crosslinking agent. In the case where the molar ratio of the monodentate organophosphine ligand to the crosslinking agent is from 0.01:1 to 10:1, the molar ratio of the monodentate organophosphine ligand to the radical initiator is from 300:1 to 10:1. Before the organic polymer mixture, the concentration of the monodentate organophosphine ligand in the organic solvent ranges from 0.01 to 1000 g/L.
The method according to claim 1, characterized in that the hydroformylation reaction of the internal olefin has a reaction temperature of 323 to 573 K, a reaction pressure of 0.1 to 10.0 MPa, a gas space velocity of 100 to 20000 h -1 , and a liquid hourly space velocity. For the range of 0.01 to 10.0 h -1 , the main components of the synthesis gas for the reaction raw materials are H 2 and CO, the volume content of (H 2 +CO) is 20-100%, and the volume ratio of H 2 /CO is 0.5-5.0. It is a C 4 -C 20 olefin, the double bond is located at positions 2 to 10 of the carbon chain, the internal olefin raw material has a purity of 20 to 100%, and the product is mainly a normal aldehyde having one carbon atom more than the raw material olefin.
The method according to claim 9, wherein the mixed gas further contains one or more of N 2 , He, CO 2 and Ar; and the raw material internal olefin further contains one of C 4 to C 20 alkane Species or more.