CN115999616A - A heterogeneous catalyst for catalyzing the hydroformylation of medium- and long-chain olefins, its preparation method and its use - Google Patents

Abstract

The invention discloses a heterogeneous catalyst for catalyzing the hydroformylation of medium and long carbon chain olefins, a preparation method and an application thereof. The catalyst is a molecular sieve encapsulated sub-nanometer cluster catalyst, including an active component and a carrier, wherein the active component is one or more of metals Rh, Co, Ir, and Au, and the carrier is all-silicon with different topological structures Molecular sieve. The active component and the carrier are combined in the form of molecular sieve encapsulating the active component. The mass of the active component elements accounts for 0.01-1.0% of the mass of the carrier. The heterogeneous catalyst provided by the present invention can catalyze the hydroformylation reaction between medium and long carbon chain olefins and synthesis gas, and prepare high-carbon aldehyde compounds. Compared with traditional hydroformylation homogeneous catalysts and disclosed The heterogeneous catalyst has a higher ratio of normal to isotropic in the product aldehyde obtained after catalytic conversion, which is beneficial to the industrial production of medium and long carbon chain normal aldehyde compounds. In addition, the catalyst of the present invention has high catalytic activity and excellent stability.

Description

A heterogeneous catalyst for catalyzing the hydroformylation of medium- and long-chain olefins, its preparation method and its use

technical field

The invention relates to a heterogeneous catalyst for catalyzing the hydroformylation of medium and long carbon chain olefins, a preparation method and an application thereof, and belongs to the field of heterogeneous catalysis.

Background technique

The hydroformylation reaction refers to the process in which alkenes and CO/ _H2 generate aldehydes under the action of a catalyst. Today, this conversion is one of the largest homogeneously catalyzed reactions in industry, with a current production capacity of more than 10 million tons per year. Aldehydes produced by hydroformylation reactions are very valuable fine chemicals and can also be converted into bulk chemicals such as alcohols, esters and amines. These bulk chemicals are the main raw materials for the synthesis of various detergents, surfactants, medicines, fragrances and other high value-added fine chemicals. The hydroformylation reaction usually leads to two types of aldehydes, namely straight-chain aldehydes and branched-chain aldehydes. Since straight-chain aldehydes are more valuable in industry, more straight-chain aldehydes are expected no matter in academic research or in the industrial field. For example, the important product of propylene hydroformylation is n-butyraldehyde, which is the raw material for the production of the most important plasticizer (Angew. Chem. Int. Ed. 2001, 40, 3408-3411).

Homogeneous catalysts have achieved remarkable results in improving the linear aldehyde selectivity (US Pat.4694109, USPat.4769498), but because the product aldehyde is in a homogeneous phase with the homogeneous catalyst, when the catalyst is recovered by means such as rectification, It is easy to cause problems such as degradation of the catalyst. Especially in the hydroformylation reaction process of medium and long chain olefins, the boiling point of the product aldehyde increases sharply with the increase of carbon number (boiling points of 1-decyl aldehyde, 1-undecanal and higher carbon number linear aldehydes all exceed 200 °C ), catalyst recovery therefore needs to be carried out at higher operating temperatures. However, high-temperature rectification and other processes will lead to the loss of ligands and the agglomeration and deactivation of the central metal, which reduces the recycling efficiency of the catalyst, thereby affecting the applicable economy.

Heterogeneous catalysts have advantages in catalyst separation and recovery and continuous production, so the development of heterogeneous catalysts to realize the hydroformylation of medium and long-chain olefins is a direction of great research value. Currently, numerous methods have been developed to realize the hydroformylation of medium and long-chain olefins in heterogeneous catalysis. For example Ding Yunjie (Catal.Sci.Technol., 2016,6,2143-2149) reported a series of catalysts based on bisphosphine ligand-based porous organic polymer loaded Rh precursor preparation, in 1-octene hydroformylation reaction Both showed good activity and selectivity for linear aldehydes. Patent CN103521268A discloses a catalyst prepared by impregnating Rh on SiO ₂ and other carriers and anchoring organic ligands. Patent CN109876847A reports a core-shell catalyst formed by supporting rhodium ions on Silicalite-1 zeolite crystal grains as seed crystals, and then epitaxially growing S-1 shell layers. High activity in 1-octene hydroformylation reaction, but low selectivity for linear aldehydes.

In general, the research and development of heterogeneous catalysts for the hydroformylation of medium and long-chain olefins is still relatively slow, mainly due to the following difficulties:

(1) The immobilization of complexes synthesized by conventional methods still has problems such as active component shedding, which leads to catalyst deactivation.

(2) The preparation of composite catalysts prepared by loading Rh complexes on organic polymers has poor heat transfer effect and low mechanical strength during the reaction process, and the organic polymers used as carriers are prone to expansion, which affects its industrial application prospects.

(3) The heterogeneous catalysts loaded on the carrier in the form of single atoms, clusters or nanoparticles have problems such as poor product control ability and low selectivity of product linear aldehydes. To sum up the above factors, if we want to realize the industrialization of heterogeneous catalysis for the hydroformylation of medium and long chain olefins, we need to develop new catalysts that can overcome the above difficulties.

Contents of the invention

Aiming at the difficulties in the development of long-chain hydroformylation catalysts, the present invention innovatively confines active metal (such as Rh) clusters in the inner pores of molecular sieves to prepare a new type of solid catalyst. The particle size of the active metal clusters in the catalyst is 0.5-1.2 nm, thereby endowing the catalyst with higher catalytic activity through the size effect. At the same time, because the active metal clusters are in the pores of the molecular sieve, it is difficult for the active components to migrate into the solution, which inhibits the loss of the active component Rh during the reaction process and improves the stability of the catalyst. In addition, the appropriate pore size of the molecular sieve matches the molecular dynamic diameter of the olefin, thereby endowing the catalyst with high selectivity to the target product linear aldehyde through the confining shape-selective effect. In view of the fact that the catalyst described in the present invention is a heterogeneous catalyst, it overcomes the shortcoming that the homogeneous catalyst and the product are difficult to separate, and simultaneously solves the problem of selectivity of the product linear aldehyde in the heterogeneous catalyst, and has industrial application value, especially in In terms of economy, it has more obvious advantages than homogeneous catalysts.

The technical problems to be solved by the present invention are: (1) to develop a novel heterogeneous catalyst, which is used to overcome the problem that the active components of the homogeneous catalyst are easy to fall off and difficult to separate. (2) Develop a heterogeneous catalyst suitable for the hydroformylation reaction of medium and long-chain olefins, and at the same time solve the problem of product linear aldehyde selectivity in the heterogeneous catalyst, that is, significantly improve the ratio of positive and negative in the product.

The technical scheme that the present invention solves the problem is:

A heterogeneous catalyst for catalyzing medium and long carbon chain olefin hydroformylation, the catalyst is a molecular sieve-encapsulated subnano cluster catalyst, composed of a catalytic active component and a carrier, wherein the catalytic active component is metal Rh, Co, Ir One, two or more of Au and Au, the carrier is a molecular sieve.

In the present invention, the medium-long carbon chain olefin refers to an olefin having 5 to 20 carbon atoms. For example, a medium-long carbon chain olefin refers to an olefin having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.

Further, the active component and the carrier are combined in the form of molecular sieves encapsulating sub-nanometer clusters of the active component. The mass of the active component elements accounts for 0.01-1.0% of the mass of the carrier, preferably 0.1-0.5%.

For example, the mass of the active component elements accounts for 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.15%, 0.2% of the mass of the carrier , 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, or 1.0%.

Further, the average particle size of the sub-nanometer clusters of the active components is 0.5-1.2 nm, for example, the average particle size of the sub-nano rhodium clusters of the active components is 0.5 nm, 0.6 nm, 0.7 nm, 0.8nm, 0.9nm, 1nm, 1.1nm or 1.2nm.

Further, the active component includes subnanometer rhodium clusters, and the average particle size of the active component subnanometer rhodium clusters is 0.5-1.2nm; for example, the average particle size of the active component subnanometer rhodium clusters is The particle size is 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1nm, 1.1nm or 1.2nm.

Further, the molecular sieve carrier is one or more of MFI, MEL, -SVR and *BEA.

Further, the molecular sieve carrier is an all-silicon molecular sieve.

Further, the catalytically active components are metals Rh and Ir. Preferably, in the catalyst, the mass ratio of metal Rh to Ir is 0.1˜10:1. For example, in the catalyst, the mass ratio of metal Rh and Ir is 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2: 1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7: 1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, 5.9:1, 6:1, 6.1:1, 6.2:1, 6.3:1, 6.4:1, 6.5:1, 6.6:1, 6.7:1, 6.8:1, 6.9:1, 7:1, 7.1:1, 7.2: 1, 7.3:1, 7.4:1, 7.5:1, 7.6:1, 7.7:1, 7.8:1, 7.9:1, 8:1, 8.1:1, 8.2:1, 8.3:1, 8.4:1, 8.5:1, 8.6:1, 8.7:1, 8.8:1, 8.9:1, 9:1, 9.1:1, 9.2:1, 9.3:1, 9.4:1, 9.5:1, 9.6:1, 9.7: 1, 9.8:1, 9.9:1, or 10:1.

Further, the catalytically active components are metal Rh and Au. Preferably, in the catalyst, the mass ratio of metal Rh to Au is 0.1˜10:1. For example, in the catalyst, the mass ratio of metal Rh to Au is 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2: 1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7: 1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, 5.9:1, 6:1, 6.1:1, 6.2:1, 6.3:1, 6.4:1, 6.5:1, 6.6:1, 6.7:1, 6.8:1, 6.9:1, 7:1, 7.1:1, 7.2: 1, 7.3:1, 7.4:1, 7.5:1, 7.6:1, 7.7:1, 7.8:1, 7.9:1, 8:1, 8.1:1, 8.2:1, 8.3:1, 8.4:1, 8.5:1, 8.6:1, 8.7:1, 8.8:1, 8.9:1, 9:1, 9.1:1, 9.2:1, 9.3:1, 9.4:1, 9.5:1, 9.6:1, 9.7: 1, 9.8:1, 9.9:1, or 10:1.

Further, the catalytically active components are metals Co and Ir. Preferably, in the catalyst, the mass ratio of metal Co and Ir is 0.1˜10:1. For example, in the catalyst, the mass ratio of metal Co and Ir is 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2: 1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7: 1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, 5.9:1, 6:1, 6.1:1, 6.2:1, 6.3:1, 6.4:1, 6.5:1, 6.6:1, 6.7:1, 6.8:1, 6.9:1, 7:1, 7.1:1, 7.2: 1, 7.3:1, 7.4:1, 7.5:1, 7.6:1, 7.7:1, 7.8:1, 7.9:1, 8:1, 8.1:1, 8.2:1, 8.3:1, 8.4:1, 8.5:1, 8.6:1, 8.7:1, 8.8:1, 8.9:1, 9:1, 9.1:1, 9.2:1, 9.3:1, 9.4:1, 9.5:1, 9.6:1, 9.7: 1, 9.8:1, 9.9:1, or 10:1.

The preparation method of the heterogeneous catalyst for the hydroformylation of medium and long carbon chain olefins in the above-mentioned catalysis comprises the following steps:

(1) Mix the water-soluble metal salt and the organic amine to obtain a mixed solution a; preferably, the water-soluble metal salt is selected from one of water-soluble rhodium salts, water-soluble cobalt salts, water-soluble iridium salts and water-soluble gold salts , two or more.

(2) Mix molecular sieve template, silicon source, optional alkali and water to obtain mixed solution b; mix mixed solution a and mixed solution b, then treat at 80°C-170°C for 10-300h, filter, Wash and dry to obtain solid powder.

(3) Calcining and reducing the solid powder obtained in step (2) to obtain a molecular sieve-encapsulated subnano cluster catalyst.

One or more of the molecular sieve templates tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide described in the technical solution step (2), used for synthesis Molecular sieves with MFI topology.

Further, in step (2), the molecular sieve template is one of 1,8-octyldiamine, tetrabutylammonium bromide, tetrabutylammonium fluoride, tetrabutylammonium hydroxide and tetrabutylphosphine hydroxide One or more kinds are used to synthesize molecular sieves with MEL topology.

Further, in step (2), the molecular sieve template is one or more of tetraethylammonium bromide, tetraethylammonium fluoride and tetraethylammonium hydroxide, used to synthesize topological molecular sieves.

Further, in step (2), the molecular sieve template is 1-methyl-1-[6-(trimethylammonium)hexyl]-pyrrolidinium ammonium difluoride, 1-methyl-1-[ 6-(Trimethylammonium)hexyl]-pyrrolidinium dihydroxide, 1,6-bis(N-methylpyrrolidine difluoride)hexane and 1,6-bis(N-methylpyrrolidine One or more of ammonium dihydroxide) hexane for the synthesis of molecular sieves with -SVR topology.

Further, in step (2), the silicon source is one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, butyl orthosilicate and sodium silicate.

Further, in step (2), the alkali is one or more of ammonia water, sodium hydroxide and potassium hydroxide.

Further, in step (1), the water-soluble rhodium salt is one or more of rhodium trichloride, rhodium nitrate, rhodium sulfate and rhodium acetate, preferably rhodium trichloride.

Further, in step (1), the water-soluble cobalt salt is one or more of cobalt dichloride, cobalt trichloride, cobalt nitrate, cobalt acetate and dicobalt octacarbonyl, preferably cobalt nitrate.

Further, in step (1), the water-soluble iridium salt is one or more of ammonium hexachloroiridate, iridium trichloride, potassium hexachloroiridate and sodium hexachloroiridate, preferably hexachloroiridate ammonium acid.

Further, in step (1), the water-soluble gold salt is one or more of gold nitrate, ammonium tetrachloroaurate, gold trichloride and sodium tetrachloroaurate, preferably ammonium tetrachloroaurate.

Further, in step (1), the organic amine is one or more of ethylenediamine, cyclohexylamine and 1,4-butanediamine, preferably ethylenediamine.

The water-soluble metal salt described in the technical solution step (1) can be rhodium trichloride, rhodium nitrate, rhodium sulfate, rhodium acetate, cobalt dichloride, cobalt trichloride, cobalt nitrate, cobalt acetate, octacarbonyl di One or more of cobalt, ammonium hexachloroiridate, iridium trichloride, potassium hexachloroiridate, sodium hexachloroiridate, gold nitrate, ammonium tetrachloroaurate, gold trichloride and sodium tetrachloroaurate preferred rhodium trichloride; preferred cobalt nitrate; preferred ammonium hexachloroiridate; preferred ammonium tetrachloroaurate. The organic amine is one or more of ethylenediamine, cyclohexylamine and 1,4-butanediamine, preferably ethylenediamine.

The calcination temperature described in step (3) of the technical solution is 450-750°C, for example, the calcination temperature is 500°C, 550°C, 600°C, 650°C, 700°C or 750°C. The calcination time is 2-20h, for example, the calcination time is 2h, 5h, 7h, 9h, 11h, 13h, 15h or 20h. The roasting atmosphere is an air atmosphere.

In step (3), the reduction temperature is 400-700°C, for example, the reduction temperature is 400°C, 450°C, 500°C, 550°C, 600°C, 650°C or 700°C. The reduction time is 3-15 hours, for example, the reduction time is 3 hours, 6 hours, 9 hours, 12 hours or 15 hours. The reducing atmosphere is a mixed atmosphere of H ₂ and N ₂ , preferably the reducing atmosphere is a 10% H ₂ /90% N ₂ atmosphere.

The use of the heterogeneous catalyst as described above or the heterogeneous catalyst prepared by any of the above methods as the hydroformylation of C5-C20 medium- and long-carbon olefins to prepare aldehydes, the medium- and long-carbon olefins Including C5~C20 medium and long carbon chain α-olefins and internal olefins. For example, the number of carbon atoms of the medium-long carbon chain olefin is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. For example, the medium-long carbon chain olefin is 1-hexene, 1-octene, 1-undecene, 2-hexene, 2-octene or 1-pentadecene.

Further, the reaction temperature of the hydroformylation reaction is 60-180°C, the reaction pressure is 2-7.0Mpa, and the reaction time is 2-24h; the reaction solvent is toluene, anisole, p-xylene and tetrahydrofuran One or more of them; the raw material gas is CO and H ₂ , and the volume ratio of CO and H ₂ in the raw material gas is 1:1-1:3.

Furthermore, the hydroformylation of medium and long carbon chain olefins to prepare aldehydes can be produced in batch mode using reactors or in continuous production using fixed beds or fluidized beds, and linear aldehyde products with an anisotropy ratio greater than 20 can be obtained. For example, the isotropic ratios for linear aldehyde products are 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1 , 30:1, 31:1, 32:1, 33:1, 34:1, 35:1, or 38:1.

Principle description of the present invention:

(1) Encapsulating the active metal component in the inner channel of the molecular sieve can make the active metal component exist in the form of sub-nanometer clusters, and the cluster size is 0.5-1.2nm, which endows the catalyst with higher catalytic performance through the size effect active.

(2) Since the active metal clusters are in the pores of the molecular sieve, it is difficult for the active components to migrate into the solution, which inhibits the loss of the active components during the reaction process and improves the stability of the catalyst.

(3) The appropriate pore size of the molecular sieve matches the molecular dynamics diameter of the olefin, and endows the catalyst with high selectivity for the target product linear aldehyde through the confining shape-selective effect.

The present invention has the following innovations and advantages:

(1) The present invention innovatively provides a heterogeneous catalyst in which molecular sieves encapsulate sub-nanometer clusters, which is used to catalyze the hydroformylation reaction of medium and long carbon chain olefins, which can easily avoid the difficult separation of products and catalysts in heterogeneous catalysis question.

(2) The catalyst provided by the invention has high catalytic activity and a very high isotropic ratio of products, and can obtain higher yields of linear aldehydes.

(3) The catalyst provided by the invention can be used repeatedly for catalysis and has very high stability.

(4) The preparation process parameters of the catalyst of the present invention are easy to control, can realize scale-up production, and have high industrialization value.

Description of drawings

Fig. 1 is the HAADF-STEM figure of 1# of embodiment 1;

Fig. 2 is the HAADF-STEM figure of 3# of embodiment 3;

Fig. 3 is the HAADF-STEM figure of 4# of embodiment 4.

Detailed ways

In order to further illustrate the technical features, objectives and beneficial effects of the present invention, the following series of examples are used to describe in detail, but not limited to this example.

HAADF-STEM images were acquired under FEI Titan3 Themis 60-300 microscope.

Remarks: The product analysis method in the examples adopts Agilent chromatographic analysis, and the specific detection methods for straight-chain aldehydes, branched-chain aldehydes and other products are:

Injection volume: 1 μL; Column temperature: 50°C for 5 minutes, 5°C/min to 100°C, hold for 5 minutes, 10°C/min to 200°C, hold for 2 minutes; inlet temperature 250°C; detector temperature : 280°C.

Septum purge gas flow: 3ml/min; column flow (N ₂ ): 1ml/min; split injection, split ratio 100:1; hydrogen flow: 40ml/min; air flow: 350ml/min; Sweep flow: 25ml/min.

Example 1

Configure 1mL of rhodium trichloride solution with a concentration of 2mol/L, add 20mmol ethylenediamine thereto, and stir to obtain solution 1; get 40g of 40wt% tetrapropylammonium hydroxide solution, add 0.5g potassium hydroxide, 42g Tetraethyl silicate and 100mL water were stirred to obtain solution 2; mixed solution 1 and solution 2; stirred at 25°C for 8h; then transferred to a 250mL stainless steel autoclave with a polytetrafluoroethylene lining, and placed at 110°C 24h, filtered, washed the solid with 30ml water three times, dried, and then calcined at 550°C for 6h in the air atmosphere, and then reduced at 400°C for 4h in the atmosphere of 10% H ₂ /90% N ₂ to prepare 0.15% Rh /MFI catalyst (the mass of Rh accounts for 0.15% of the mass of the MFI molecular sieve carrier), denoted as number 1#. Figure 1 is the HAADF-STEM image of 1# in Example 1, which is the image of Rh nanoparticles measured by FEI Titan ³ Themis 60-300 at a voltage of 300kV. In this sample, most of ~1nm Rh is encapsulated in In the channels of MFI molecular sieves.

100 mmol of reaction substrate 1-hexene, 200 ml of toluene reaction solvent, and 2 g of 0.15% Rh/MFI catalyst were sequentially put into the autoclave. The air in the autoclave was replaced with CO several times. After the replacement, CO and H ₂ were filled with a total pressure of 5 MPa and a volume ratio of 1:1. React at 85° C. for 6 h, wait until the reactor is cooled to room temperature, and perform chromatographic quantitative analysis on the mixture. Table 1 shows the reaction results of catalyst-catalyzed hydroformylation of olefins.

Example 2

Prepare 1mL of cobalt nitrate solution with a concentration of 2mol/L, add 20mmol ethylenediamine to it, and stir to obtain solution 3; the configuration is the same as solution 2 in Example 1; mix solution 3 and solution 2; stir at 25°C for 8h, and then transfer Put it in a 250mL stainless steel autoclave with a polytetrafluoroethylene lining, place it at 110°C for 24h, filter, wash the solid with 30ml of water three times, dry it, and then roast it at 550°C for 6h in an air atmosphere, and then in 10 In %H ₂ /90% N ₂ atmosphere, reduction at 400°C for 4 hours prepared a 0.15% Co/MFI catalyst (the mass of Co accounted for 0.15% of the mass of the MFI molecular sieve carrier), which was designated as No. 2#.

100 mmol of reaction substrate 1-hexene, 200 ml of toluene reaction solvent, and 2 g of 0.15% Co/MFI catalyst were sequentially put into the autoclave. The air in the autoclave was replaced with CO several times. After the replacement, CO and H ₂ were filled with a total pressure of 5 MPa and a volume ratio of 1:1. React at 160° C. for 18 h, wait for the reactor to cool down to room temperature, and perform chromatographic quantitative analysis on the mixture. Table 1 shows the reaction results of catalyst-catalyzed hydroformylation of olefins.

Example 3

Configuration 1mL concentration is the rhodium trichloride solution of 2mol/L, 1mL concentration is the ammonium hexachloroiridate solution of 2mol/L, adds 20mmol ethylenediamine thereinto respectively, mixes, stirs, obtains solution 4; Configuration is with embodiment 1 Solution 2 in the solution; mixed solution 4 and solution 2, stirred at 30°C for 8h, then transferred to a 250mL stainless steel autoclave with PTFE lining, placed at 110°C for 24h, filtered, and the solid was washed three times with 30ml of water , dried, and then calcined at 550°C for 6h in an air atmosphere, and then reduced at 400°C for 4h in a 10%H ₂ /90%N ₂ atmosphere to prepare a 0.15%Rh-0.15%Ir/MFI catalyst (Rh mass Accounting for 0.15% of the mass of the MFI molecular sieve carrier, Ir mass accounting for 0.15% of the mass of the MFI molecular sieve carrier), recorded as number 3#. Figure 2 is the HAADF-STEM image of 3# in Example 3; it is the image of Rh nanoparticles and Ir nanoparticles measured at a voltage of 300kV by FEI Titan ³ Themis 60-300, most of the ~1nm particles in this sample Rh and ~1nm Ir are encapsulated in the channels of MFI molecular sieves.

100 mmol of reaction substrate 1-hexene, 200 ml of toluene reaction solvent, and 2 g of 0.15% Rh-0.15% Ir/MFI catalyst were sequentially put into the autoclave. The air in the autoclave was replaced with CO several times. After the replacement, CO and H ₂ were filled with a total pressure of 5 MPa and a volume ratio of 1:1. React at 85° C. for 6 h, wait until the reactor is cooled to room temperature, and perform chromatographic quantitative analysis on the mixture. Table 1 shows the reaction results of catalyst-catalyzed hydroformylation of olefins.

Example 4

Configuration 1mL concentration is the rhodium trichloride solution of 2mol/L, 1mL concentration is the ammonium tetrachloroaurate solution of 2mol/L, adds 20mmol ethylenediamine thereinto respectively, mixes, stirs, obtains solution 5; Configuration is with embodiment 1 Solution 2 in the solution; mixed solution 5 and solution 2, stirred at 30°C for 8h, then transferred to a 250mL stainless steel autoclave with PTFE lining, placed at 110°C for 24h, filtered, and the solid was washed three times with 30ml of water , dried, and then calcined at 550°C for 6h in an air atmosphere, and then reduced at 400°C for 4h in a 10%H ₂ /90%N ₂ atmosphere to prepare a 0.15%Rh-0.15%Au/MFI catalyst (Rh mass accounted for 0.15% of the mass of the MFI molecular sieve carrier, and the mass of Au accounted for 0.15% of the mass of the MFI molecular sieve carrier), recorded as number 4#. Fig. 3 is the HAADF-STEM figure of 4# of embodiment 4. It is the image of Rh nanoparticles and Au nanoparticles measured by FEI Titan ³ Themis 60-300 at 300kV voltage. In this sample, most of ~1nm Rh and ~1nm Au are encapsulated in the channels of MFI molecular sieves.

100 mmol of reaction substrate 1-hexene, 200 ml of toluene reaction solvent, and 2 g of 0.15% Rh-0.15% Au/MFI catalyst were sequentially put into the autoclave. The air in the autoclave was replaced with CO several times. After the replacement, CO and H ₂ were filled with a total pressure of 5 MPa and a volume ratio of 1:1. React at 85° C. for 6 h, wait until the reactor is cooled to room temperature, and perform chromatographic quantitative analysis on the mixture. Table 1 shows the reaction results of catalyst-catalyzed hydroformylation of olefins.

Example 5

Configuration is the same as solution 1 in Example 1; get 39g of 40wt% tetrabutylammonium hydroxide solution, add 0.4g potassium hydroxide, 42g tetraethyl silicate, 13mL water, stir to obtain solution 6; mix solution 1 and solution 6. Stir at 30°C for 12h, then transfer to a 250mL stainless steel autoclave with PTFE lining, place it at 130°C for 30h, filter, wash the solid with 30ml of water three times, dry, and then in air atmosphere, in Calcined at 550°C for 8h, then reduced at 500°C for 4h in a 10% _H2 /90% _N2 atmosphere to prepare a 0.15% Rh/MEL catalyst (the mass of Rh accounted for 0.15% of the mass of the MEL molecular sieve carrier), which was designated as No. 5 #.

100 mmol of reaction substrate 1-hexene, 200 ml of toluene reaction solvent, and 2 g of 0.15% Rh/MEL catalyst were sequentially put into the autoclave. The air in the autoclave was replaced with CO several times. After the replacement, CO and H ₂ were filled with a total pressure of 5 MPa and a volume ratio of 1:1. React at 85° C. for 6 h, wait until the reactor is cooled to room temperature, and perform chromatographic quantitative analysis on the mixture. Table 1 shows the reaction results of catalyst-catalyzed hydroformylation of olefins.

Example 6

The configuration is the same as solution 1 in Example 1; take 16.2g of tetraethylammonium fluoride, add 30g of water, stir, then add 0.5g of sodium hydroxide, 42g of tetraethyl silicate, stir at 25°C for 6h, add solution 1, Stir for another 2h; then transfer to a 250mL stainless steel autoclave with PTFE lining, place it at 140°C for 48h, filter, wash the solid with 30ml of water three times, dry, and then in the air atmosphere, at 550°C Calcined for 8 hours, then reduced in 10% H ₂ /90% N ₂ atmosphere at 500°C for 4 hours to prepare a 0.15% Rh/*BEA catalyst (the mass of Rh accounted for 0.15% of the mass of the *BEA molecular sieve carrier), which was designated as No. 6# .

100 mmol of reaction substrate 1-hexene, 200 ml of toluene reaction solvent, and 2 g of 0.15% Rh/*BEA catalyst were sequentially put into the autoclave. The air in the autoclave was replaced with CO several times. After the replacement, CO and H ₂ were filled with a total pressure of 5 MPa and a volume ratio of 1:1. React at 85° C. for 6 h, wait until the reactor is cooled to room temperature, and perform chromatographic quantitative analysis on the mixture. Table 1 shows the reaction results of catalyst-catalyzed hydroformylation of olefins.

Example 7

The configuration is the same as solution 1 in Example 1; take 28.8g of 1,6-bis(N-methylpyrrolidine ammonium dihydroxide) hexane, add 120mL of water, stir, then add 42g of tetraethyl silicate, at 30°C Stir for 24 hours, remove the ethanol produced during this period, add solution 1, and stir for another 2 hours; then transfer to a 250mL stainless steel autoclave with a polytetrafluoroethylene lining, place it at 170°C for 300 hours, filter, and wash the solid with 30ml of water three times , dried, then calcined at 550°C for 8h in an air atmosphere, and then reduced at 500°C for 6h in a 10%H ₂ /90%N ₂ atmosphere to prepare a 0.15%Rh/-SVR catalyst (Rh mass accounted for-SVR 0.15% of the mass of the molecular sieve carrier), denoted as number 7#.

100 mmol of reaction substrate 1-hexene, 200 ml of toluene reaction solvent, and 2 g of 0.15% Rh/-SVR catalyst were sequentially put into the autoclave. The air in the autoclave was replaced with CO several times. After the replacement, CO and H ₂ were filled with a total pressure of 5 MPa and a volume ratio of 1:1. React at 85° C. for 6 h, wait until the reactor is cooled to room temperature, and perform chromatographic quantitative analysis on the mixture. Table 1 shows the reaction results of catalyst-catalyzed hydroformylation of olefins.

Example 8

Configure 1mL of cobalt nitrate solution with a concentration of 2mol/L, and 1mL of ammonium hexachloroiridate solution with a concentration of 2mol/L, add 20mmol ethylenediamine to it respectively, mix and stir to obtain solution 7; take 28.8g 1,6- Add 120 mL of water to bis(N-methylpyrrolidine ammonium dihydroxide) hexane, stir, then add 42 g of tetraethyl silicate, stir at 30°C for 24 h, remove the ethanol produced during this period, add solution 7, and stir for another 2 h; Then transfer to a 250mL stainless steel autoclave with polytetrafluoroethylene lining, place it at 170°C for 300h, filter, wash the solid with 30ml of water three times, dry it, and roast it at 550°C for 8h in an air atmosphere, then Reduction at 500°C for 6 hours prepared a 0.15% Co-0.15% Ir/-SVR catalyst (the mass of Co accounted for 0.15% of the mass of the -SVR molecular sieve carrier, and the mass of Ir accounted for 0.15% of the mass of the -SVR molecular sieve carrier), which was recorded as No. 8#.

100 mmol of reaction substrate 1-hexene, 200 ml of toluene reaction solvent, and 2 g of 0.15% Co-0.15% Ir/-SVR catalyst were sequentially put into the autoclave. The air in the autoclave was replaced with CO several times. After the replacement, CO and H ₂ were filled with a total pressure of 5 MPa and a volume ratio of 1:1. React at 160° C. for 18 h, wait for the reactor to cool down to room temperature, and perform chromatographic quantitative analysis on the mixture. Table 1 shows the reaction results of catalyst-catalyzed hydroformylation of olefins.

Example 9

The substrate for evaluation is replaced with 1-octene, and the others are the same as in Example 1.

Example 10

The substrate for evaluation is replaced with 1-undecene, and the others are the same as in Example 1.

Example 11

The substrate for evaluation was replaced with 1-pentadecene, and the others were the same as in Example 1.

Example 12

The substrate for evaluation is replaced with 2-hexene, and the others are the same as in Example 1.

Example 13

The substrate for evaluation is replaced with 2-octene, and the others are the same as in Example 1.

Comparative example 1

Utilizing impregnation method, 0.15wt% Rh rhodium trichloride solution is impregnated on 20g of silica support, then dried, baked at 550°C for 6h in air atmosphere, and then heated in 10% H ₂ /90% In N ₂ atmosphere, reduce at 400°C for 4 hours to obtain a 0.15% Rh-SiO ₂ catalyst (the mass of Rh accounts for 0.15% of the mass of the SiO ₂ carrier).

100 mmol of reaction substrate 1-hexene, 200 ml of toluene reaction solvent, and 2 g of 0.15% Rh-SiO ₂ catalyst were successively put into the autoclave. The air in the autoclave was replaced with CO several times. After the replacement, CO and H ₂ were filled with a total pressure of 5 MPa and a volume ratio of 1:1. React at 85° C. for 6 h, wait until the reactor is cooled to room temperature, and perform chromatographic quantitative analysis on the mixture. Table 1 shows the reaction results of catalyst-catalyzed hydroformylation of olefins.

Comparative example 2

Take 40g of 40wt% tetrapropylammonium hydroxide solution, add 0.5g potassium hydroxide, 42g tetraethyl silicate, 100mL water, stir at 25°C for 8h; In a high-pressure reactor, place it at 110°C for 24h, filter, wash the solid with 30ml of water three times, dry it, and then calcinate it at 550°C for 6h in an air atmosphere to obtain the MFI carrier. Using the impregnation method, 0.15wt% Rh rhodium trichloride solution was impregnated on 20g of MFI carrier, then dried, then calcined at 550°C for 6h in air atmosphere, and then in 10% _H2 /90%N ₂ atmosphere, 400° C. for 4 h to obtain a 0.15% Rh-MFI catalyst (the mass of Rh accounts for 0.15% of the mass of the carrier).

100 mmol of reaction substrate 1-hexene, 200 ml of toluene reaction solvent, and 2 g of 0.15% Rh-MFI catalyst were sequentially put into the autoclave. The air in the autoclave was replaced with CO several times. After the replacement, CO and H ₂ were filled with a total pressure of 5 MPa and a volume ratio of 1:1. React at 85° C. for 6 h, wait until the reactor is cooled to room temperature, and perform chromatographic quantitative analysis on the mixture. Table 1 shows the reaction results of catalyst-catalyzed hydroformylation of olefins.

Table 1 The reaction results of olefin hydroformylation catalyzed by various catalysts

It can be seen from the above table that the heterogeneous catalyst provided by the present invention is suitable for the hydroformylation reaction of C5-C20 medium and long carbon chain olefins, and has the characteristics of high catalytic activity, high selectivity and very high product positive-to-isotropic ratio. Important industrial application value.

Parts not described in detail in the present invention belong to the known techniques of those skilled in the art. The above-mentioned embodiments are only descriptions of the preferred implementations of the present invention, and the preferred embodiments do not exhaustively describe all the details, nor limit the invention to the described specific implementations. Without departing from the design spirit of the present invention, various modifications and improvements to the technical solution of the present invention by those skilled in the art shall fall within the scope of protection determined by the claims of the present invention.

Claims (10)

1. A heterogeneous catalyst for catalyzing medium and long carbon chain olefin hydroformylation, characterized in that: the catalyst is a molecular sieve encapsulated sub-nanometer cluster catalyst, consisting of a catalytically active component and a carrier, wherein the catalytically active component is One, two or more of metals Rh, Co, Ir and Au, and the carrier is molecular sieve. 2. The heterogeneous catalyst according to claim 1, characterized in that: between the active component and the carrier, the combination is realized in the form of molecular sieve encapsulating active component sub-nanometer clusters; the active component element The mass accounts for 0.01-1.0% of the mass of the carrier, preferably 0.1-0.5%; the average particle size of the active component sub-nano clusters is 0.5-1.2nm. 3. The heterogeneous catalyst according to any one of claims 1-2, characterized in that: the molecular sieve carrier is one or more of MFI, MEL, -SVR and *BEA; preferably the The molecular sieve carrier is a hydrophobic all-silicon molecular sieve; Preferably, the catalytically active component is metal Rh and Ir, more preferably the mass ratio of metal Rh and Ir is 0.1-10:1; Preferably, the catalytically active component is metal Rh and Au, more preferably the mass ratio of metal Rh and Au is 0.1-10:1; Preferably, the catalytically active components are metal Co and Ir, more preferably the mass ratio of metal Co and Ir is 0.1˜10:1. 4. the preparation method of catalyst described in claim 1 is characterized in that, comprises the following steps: (1) Mix the water-soluble metal salt and the organic amine to obtain a mixed solution a; preferably, the water-soluble metal salt is selected from one of water-soluble rhodium salts, water-soluble cobalt salts, water-soluble iridium salts and water-soluble gold salts , two or more; (2) mixing molecular sieve template, silicon source, optional alkali and water to obtain mixed solution b; Mix the mixed solution a and the mixed solution b, then treat at 80°C to 170°C for 10 to 300 hours, filter, wash and dry to obtain a solid powder; (3) Calcining and reducing the solid powder obtained in step (2) to obtain a molecular sieve-encapsulated subnano cluster catalyst. 5. The method according to claim 4, characterized in that: In step (2), the molecular sieve template is one or more of tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide, which is used to synthesize Molecular sieve with MFI topology; or, the molecular sieve template is one of 1,8-octyl diamine, tetrabutylammonium bromide, tetrabutylammonium fluoride, tetrabutylammonium hydroxide and tetrabutylphosphine hydroxide or more, for synthesizing a molecular sieve with a MEL topology; or, the molecular sieve template is one or more of tetraethylammonium bromide, tetraethylammonium fluoride and tetraethylammonium hydroxide , for synthesizing a molecular sieve with *BEA topology; or, the molecular sieve template is 1-methyl-1-[6-(trimethylammonium)hexyl]-pyrrolidinium ammonium difluoride, 1-methyl Base-1-[6-(trimethylammonium)hexyl]-pyrrolidinium ammonium dihydroxide, 1,6-bis(N-methylpyrrolidine difluoride)hexane and 1,6-bis(N - one or more of methylpyrrolidine ammonium hydroxide) hexane, used to synthesize molecular sieves with -SVR topological structure; preferably the silicon source is tetramethyl orthosilicate, tetraethyl silicate One or more of ester, butyl orthosilicate and sodium silicate; preferably the alkali is one or more of ammonia water, sodium hydroxide and potassium hydroxide. 6. method according to claim 4, is characterized in that: in step (1), described water-soluble rhodium salt is one or more in rhodium trichloride, rhodium nitrate, rhodium sulfate and rhodium acetate, Rhodium trichloride is preferred; The water-soluble cobalt salt is one or more of cobalt dichloride, cobalt trichloride, cobalt nitrate, cobalt acetate and dicobalt octacarbonyl, preferably cobalt nitrate; The water-soluble iridium salt is one or more of ammonium hexachloroiridate, iridium trichloride, potassium hexachloroiridate and sodium hexachloroiridate, preferably ammonium hexachloroiridate; The water-soluble gold salt is one or more of gold nitrate, ammonium tetrachloroaurate, gold trichloride and sodium tetrachloroaurate, preferably ammonium tetrachloroaurate; Preferably, the organic amine is one or more of ethylenediamine, cyclohexylamine and 1,4-butanediamine, more preferably ethylenediamine. 7. The method according to claim 4, characterized in that: in step (3), the calcination temperature is 450-750°C, the calcination time is 2-20h, and the calcination atmosphere is an air atmosphere; preferably, the The reduction temperature is 400-700° C., the reduction time is 3-15 hours, and the reducing atmosphere is a mixture of H ₂ and N ₂ , preferably a 10% H ₂ /90% N ₂ atmosphere. 8. The heterogeneous catalyst described in any one of claims 1-3 or the heterogeneous catalyst prepared by the method described in any one of claims 4-7 is used as the hydroformylation preparation of medium and long carbon chain olefins of C5～C20 The use of aldehydes is characterized in that the medium and long carbon chain olefins include C5-C20 medium and long carbon chain α-olefins and internal olefins. 9. The use according to claim 8, characterized in that: the reaction temperature of the hydroformylation reaction is 60-180°C, the reaction pressure is 2-7.0Mpa, and the reaction time is 2-24h; the preferred reaction The solvent is one or more of toluene, anisole, p-xylene and tetrahydrofuran; the preferred volume ratio of CO and _H in the feed gas is 1:1-1:3. 10. purposes according to claim 8, it is characterized in that: medium-long carbon chain olefin hydroformylation prepares aldehyde reaction to use reaction kettle batch type production or utilize fixed bed, fluidized bed to carry out continuous production, obtain positive-to-isotropic ratio greater than 20 linear aldehyde products.

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