CN115999616A - Heterogeneous catalyst for catalyzing long and medium carbon chain olefin hydroformylation, preparation method and application thereof - Google Patents

Heterogeneous catalyst for catalyzing long and medium carbon chain olefin hydroformylation, preparation method and application thereof Download PDF

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CN115999616A
CN115999616A CN202310053845.6A CN202310053845A CN115999616A CN 115999616 A CN115999616 A CN 115999616A CN 202310053845 A CN202310053845 A CN 202310053845A CN 115999616 A CN115999616 A CN 115999616A
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molecular sieve
catalyst
water
carrier
active component
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曹直
闫涛
张湘杰
万红柳
宫能锋
孙晓东
何鹏
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Shanxi Institute of Coal Chemistry of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses a heterogeneous catalyst for catalyzing long and medium carbon chain olefin hydroformylation, a preparation method and application thereof. The catalyst is a molecular sieve encapsulated sub-nanocluster catalyst and comprises an active component and a carrier, wherein the active component is one or more of metals Rh, co, ir, au, and the carrier is an all-silicon molecular sieve with different topological structures. The active components and the carrier are combined in a form of encapsulating the active components by a molecular sieve. The mass of the active component element accounts for 0.01 to 1.0 percent of the mass of the carrier. The heterogeneous catalyst provided by the invention can catalyze the long and medium carbon chain olefin to generate a hydroformylation reaction with the synthesis gas to prepare the high-carbon aldehyde compound, and compared with the traditional hydroformylation homogeneous catalyst and the disclosed heterogeneous catalyst, the heterogeneous catalyst has higher normal-to-iso ratio in the product aldehyde obtained after catalytic conversion, and is beneficial to industrial production of the long and medium carbon chain normal-structure aldehyde compound. In addition, the catalyst provided by the invention has higher catalytic activity and excellent stability.

Description

Heterogeneous catalyst for catalyzing long and medium carbon chain olefin hydroformylation, preparation method and application thereof
Technical Field
The invention relates to a heterogeneous catalyst for catalyzing long and medium carbon chain olefin hydroformylation, a preparation method and application thereof, and belongs to the field of heterogeneous catalysis.
Background
Hydroformylation refers to olefins and CO/H 2 And (3) generating aldehyde under the action of the catalyst. Today, this conversion is one of the largest industrially homogeneous catalytic reactions, with annual capacity exceeding 1000 ten thousand tons. Aldehydes produced by hydroformylation are very valuable fine chemicals, also converted to bulk chemicals such as alcohols, esters and amines. These bulk chemicals are the main raw materials for synthesizing various detergents, surfactants, medicines, fragrances and the like, which are highly additional valuable fine chemicals. The hydroformylation reaction typically yields two classes of aldehydes, namely, linear aldehydes and branched aldehydes. Since linear aldehydes are of greater industrial value, more linear aldehydes are desired, both in academic research and in industrial fields. An important product for the hydroformylation of propylene is, for example, n-butyraldehyde, which is the starting material for the production of the plasticizers of the greatest importance at present (Angew. Chem. Int. Ed.2001,40, 3408-3411).
While homogeneous catalysts have achieved remarkable results in improving the selectivity of linear aldehydes (US Pat.4694109, US Pat. 4769498), the product aldehydes are in a homogeneous phase with the homogeneous catalyst, which is prone to problems such as degradation of the catalyst when the catalyst is recovered by means of rectification or the like. In particular, in the hydroformylation process of long-chain and medium-chain olefins, the boiling point of the product aldehyde increases sharply with the increase of the carbon number (the boiling points of 1-decanal, 1-undecalaldehyde and higher straight-chain aldehydes all exceed 200 ℃), and the recovery and utilization of the catalyst are required to be carried out at a higher operating temperature. However, the processes of high-temperature rectification and the like can lead to ligand falling and central metal agglomeration and inactivation, so that the recycling efficiency of the catalyst is reduced, and the application economy is affected.
Heterogeneous catalysts have advantages in catalyst separation and recovery and continuous production, so the development of heterogeneous catalysts to achieve hydroformylation of long-chain olefins is a valuable direction of research. Currently, numerous processes are developed to effect heterogeneously catalyzed hydroformylation of long chain olefins. For example Ding Yunjie (Catal. Sci. Technology., 2016,6,2143-2149) reports that a series of catalysts prepared by loading Rh precursors with porous organic polymers based on bisphosphine ligands show better activity and linear aldehyde selectivity in the hydroformylation of 1-octene. Published SiO in patent CN103521268A 2 A catalyst prepared by a method of impregnating Rh with an organic ligand. The patent CN109876847A reports a core-shell catalyst formed by epitaxially growing an S-1 shell layer by taking rhodium ions loaded on Silicalite-1 zeolite crystal grains as seed crystals. The activity in the hydroformylation of 1-octene is high, but the selectivity of linear aldehyde is low.
Overall, heterogeneous catalysts for the hydroformylation of long and medium chain olefins are still relatively slow to develop, mainly with the following difficulties:
(1) The complex synthesized by the conventional method still has the problems of falling of active components and the like, and the catalyst is deactivated.
(2) The Rh complex is loaded on the organic polymer to prepare the composite catalyst, so that the composite catalyst has poor heat transfer effect and low mechanical strength in the reaction process, and the organic polymer serving as a carrier is easy to expand, so that the industrial application prospect of the composite catalyst is influenced.
(3) Heterogeneous catalysts loaded on a carrier in the form of single atoms, clusters or nano particles have the problems of poor product regulation and control capability, low selectivity of linear aldehyde of a product and the like. In view of various factors, if heterogeneous catalytic industrialization of the hydroformylation of long-chain and medium-chain olefins is desired, a novel catalyst capable of overcoming the above-mentioned difficulties has been desired.
Disclosure of Invention
Aiming at the difficulty in developing a long-chain hydroformylation catalyst, the invention creatively limits active metal (such as Rh) clusters in a pore canal in a molecular sieve to prepare a novel solid catalyst. The active metal cluster particles in the catalyst are 0.5-1.2 nm, so that the catalyst has higher catalytic activity through the size effect. Meanwhile, as the active metal clusters are in the molecular sieve pore channels, active components are difficult to migrate into the solution, so that the loss of active components Rh in the reaction process is inhibited, and the stability of the catalyst is improved. In addition, the pore size of the molecular sieve is matched with the molecular dynamics diameter of olefin, so that the catalyst is endowed with high selectivity to target product linear aldehyde through a finite field shape selective effect. In view of the fact that the catalyst is a heterogeneous catalyst, the method overcomes the defect that a homogeneous catalyst is difficult to separate from a product, solves the problem of selectivity of linear aldehyde of the product in the heterogeneous catalyst, has industrial application value, and particularly has obvious advantages in economical aspect compared with the homogeneous catalyst.
The technical problems to be solved by the invention are as follows: (1) A novel heterogeneous catalyst is developed for overcoming the problems that the active components of the homogeneous catalyst are easy to fall off and difficult to separate. (2) The heterogeneous catalyst suitable for the hydroformylation of the medium-long carbon chain olefins is developed, and meanwhile, the problem of the selectivity of the linear aldehyde of the product in the heterogeneous catalyst is solved, namely, the normal-to-iso ratio in the product is obviously improved.
The technical scheme for solving the problems is as follows:
a heterogeneous catalyst for catalyzing the hydroformylation of medium-long carbon chain olefins is a molecular sieve encapsulated sub-nanocluster catalyst and consists of a catalytic active component and a carrier, wherein the catalytic active component is one, two or more of metal Rh, co, ir and Au, and the carrier is a molecular sieve.
In the present invention, the medium-long carbon chain olefin means an olefin having 5 to 20 carbon atoms. For example, medium and long carbon chain olefins refer to olefins having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms.
Further, the active components and the carrier are combined in a mode of molecular sieve encapsulation of active component sub-nanoclusters. The mass of the active component element accounts for 0.01 to 1.0 percent of the mass of the carrier, and is preferably 0.1 to 0.5 percent.
For example, the active component element comprises 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.15%, 0.2%, 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% of the carrier by mass.
Further, the average particle size of the active component sub-nano-clusters is 0.5-1.2 nm, for example, the average particle size of the active component sub-nano-rhodium clusters is 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1nm, 1.1nm or 1.2nm.
Further, the active component comprises sub-nanometer rhodium clusters, and the average particle size of the sub-nanometer rhodium clusters of the active component is 0.5-1.2 nm; for example, the average particle size of the active component sub-nano rhodium clusters 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 component is the metals Rh and Ir. Preferably, in the catalyst, the mass ratio of the metal Rh to the Ir is 0.1-10:1. For example, in the catalyst, the metal Rh and Ir mass ratio 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, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4:1, 4.4:1, 4:1, 4.1, 4:1, 4.4:1, 4.1, 4:1); 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, 6.1:1: 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 the metals Rh and Au. Preferably, in the catalyst, the mass ratio of the metal Rh to the metal 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, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4:1, 4.4:1, 4:1, 4.1, 4:1, 4.4:1, 4.1, 4:1, 4.4:1); 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, 6.1:1: 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 the metal Co to the Ir is 0.1-10:1. For example, in the catalyst, the mass ratio of metal Co to 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, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4:1, 4.4:1, 4:1, 4.1, 4:1, 4.4:1, 4.1, 4:1, 4.4:1, 4.1); 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, 6.1:1: 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 multi-phase catalyst for catalyzing the hydroformylation of the medium-long carbon chain olefins comprises the following steps:
(1) Mixing water-soluble metal salt and organic amine to obtain a mixed solution a; preferably, the water-soluble metal salt is selected from one, two or more of a water-soluble rhodium salt, a water-soluble cobalt salt, a water-soluble iridium salt and a water-soluble gold salt.
(2) Mixing a molecular sieve template agent, a silicon source, optional alkali and water to obtain a mixed solution b; mixing the mixed solution a and the mixed solution b, then treating for 10-300 h at the temperature of 80-170 ℃, filtering, washing and drying to obtain solid powder.
(3) And (3) roasting and reducing the solid powder obtained in the step (2) to obtain the molecular sieve encapsulated sub-nanocluster catalyst.
The molecular sieve template agent in the step (2) of the technical scheme is one or more of tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide, and is used for synthesizing the molecular sieve with the MFI topological structure.
Further, in the step (2), the molecular sieve template agent is one or more of 1, 8-octanediamine, tetrabutylammonium bromide, tetrabutylammonium fluoride, tetrabutylammonium hydroxide and tetrabutylphosphine hydroxide, and is used for synthesizing the molecular sieve with the MEL topological structure.
Further, in the step (2), the molecular sieve template agent is one or more of tetraethylammonium bromide, tetraethylammonium fluoride and tetraethylammonium hydroxide, and is used for synthesizing the molecular sieve with the BEA topological structure.
Further, in the step (2), the molecular sieve template agent is one or more of 1-methyl-1- [6- (trimethylammonium) hexyl ] -pyrrolidine ammonium difluoride, 1-methyl-1- [6- (trimethylammonium) hexyl ] -pyrrolidine ammonium hydroxide, 1, 6-bis (N-methylpyrrolidine ammonium difluoride) hexane and 1, 6-bis (N-methylpyrrolidine ammonium hydroxide) hexane, and is used for synthesizing the molecular sieve with the-SVR topological structure.
Further, in the step (2), the silicon source is one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, butyl orthosilicate, sodium silicate and the like.
Further, in the step (2), the alkali is one or more of ammonia water, sodium hydroxide and potassium hydroxide.
Further, in the 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 the step (1), the water-soluble cobalt salt is one or more of cobalt dichloride, cobalt trichloride, cobalt nitrate, cobalt acetate and cobalt octacarbonyl, preferably cobalt nitrate.
Further, in the step (1), the water-soluble iridium salt is one or more of ammonium hexachloroiridate, iridium trichloride, potassium hexachloroiridate and sodium hexachloroiridate, preferably ammonium hexachloroiridate.
Further, in the 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 the step (1), the organic amine is one or more of ethylenediamine, cyclohexylamine and 1, 4-butanediamine, preferably ethylenediamine.
The water-soluble metal salt in the step (1) of the technical scheme can be one or more of rhodium trichloride, rhodium nitrate, rhodium sulfate, rhodium acetate, cobalt dichloride, cobalt trichloride, cobalt nitrate, cobalt acetate, cobalt octacarbonyl, ammonium hexachloroiridate, iridium trichloride, potassium hexachloroiridate, sodium hexachloroiridate, gold nitrate, ammonium tetrachloroaurate, gold trichloride and sodium tetrachloroaurate; rhodium trichloride is preferred; cobalt nitrate is preferred; ammonium hexachloroiridium is preferred; ammonium tetrachloroaurate is preferred. The organic amine is one or more of ethylenediamine, cyclohexylamine and 1, 4-butanediamine, preferably ethylenediamine.
The baking temperature in the step (3) of the technical proposal is 450-750 ℃, for example, the baking temperature is 500 ℃,550 ℃, 600 ℃, 650 ℃, 700 ℃ or 750 ℃. The roasting time is 2-20 h, for example, 2h, 5h, 7h, 9h, 11h, 13h, 15h or 20h. The roasting atmosphere is an air atmosphere.
In the step (3), the reduction temperature is 400 to 700 ℃, for example, 400 ℃, 450 ℃,500 ℃,550 ℃, 600 ℃, 650 ℃ or 700 ℃. The reduction time is 3 to 15 hours, for example 3 hours, 6 hours, 9 hours, 12 hours or 15 hours. Reducing atmosphere to H 2 And N 2 The mixing atmosphere, preferably the reducing atmosphere is 10% H 2 /90％N 2 Atmosphere.
Use of a heterogeneous catalyst as defined in any one of the preceding claims or a heterogeneous catalyst prepared by a process as defined in any one of the preceding claims as a C5 to C20 medium long carbon chain olefin comprising C5 to C20 medium long carbon chain alpha-olefins and internal olefins for the hydroformylation of the medium long carbon chain olefins to produce aldehydes. For example, the medium and long carbon chain olefins have 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. For example, the medium and 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 ℃, the reaction pressure is 2-7.0 Mpa, and the reaction time is 2-24 h; the reaction solvent is one or more of toluene, anisole, paraxylene and tetrahydrofuran; the raw material gas is CO and H 2 CO and H in the feed gas 2 The volume ratio of (2) is 1:1-1:3.
Further, the reaction for preparing aldehyde by hydroformylation of long and medium carbon chain olefins uses a reaction kettle for intermittent production or uses a fixed bed and a fluidized bed for continuous production, and a linear aldehyde product with the positive-to-negative ratio of more than 20 can be obtained. For example, the normal to iso ratio of the linear aldehyde product is 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.
Description of the principles of the invention:
(1) The active metal component is encapsulated in the pore canal of the molecular sieve, so that the active metal component exists in the form of sub-nanometer clusters, the cluster size is 0.5-1.2 nm, and the catalyst is endowed with higher catalytic activity through the size effect.
(2) Because the active metal clusters are in the molecular sieve pore channels, active components are difficult to migrate into the solution, the loss of the active components in the reaction process is inhibited, and the stability of the catalyst is improved.
(3) The pore diameter of the molecular sieve is matched with the molecular dynamics diameter of olefin, and the catalyst is endowed with high selectivity to target product linear aldehyde through a finite field shape selective effect.
The invention has the following innovation points and advantages:
(1) The invention innovatively provides a heterogeneous catalyst of molecular sieve encapsulated sub-nanoclusters, which is used for catalyzing the hydroformylation reaction of medium-long carbon chain olefins, and can easily avoid the problem of difficult separation of products and catalysts in heterogeneous catalysis.
(2) The catalyst provided by the invention has higher catalytic activity and very high positive-to-negative ratio of the product, and can obtain higher yield of the linear aldehyde.
(3) The catalyst provided by the invention can be repeatedly recycled for catalysis, and has very high stability.
(4) The preparation process parameters of the catalyst are easy to regulate and control, can realize amplified production, and have higher industrialization value.
Drawings
FIG. 1 is a HAADF-STEM diagram of example 1# 1;
FIG. 2 is a HAADF-STEM diagram of example 3# 3;
FIG. 3 is a HAADF-STEM diagram of example 4# 4.
Detailed Description
For further explanation of technical features, objects and advantageous effects of the present invention, the following series of embodiments are described in detail, but are not limited to the present embodiment.
HAADF-STEM images were obtained under a FEI Titan3 Themis 60-300 microscope.
Remarks: the product analysis method in the embodiment adopts Agilent chromatography analysis, and the specific detection method of the linear aldehyde, the branched aldehyde and other products comprises the following steps:
sample injection amount: 1 μl; column temperature: maintaining at 50deg.C for 5min, heating to 100deg.C at 5deg.C/min, maintaining for 5min, heating to 200deg.C at 10deg.C/min, and maintaining for 2min; the temperature of the sample inlet is 250 ℃; detector temperature: 280 ℃.
Spacer purge gas flow rate: 3ml/min; chromatographic column flow Rate (N) 2 ): 1ml/min; split sample injection, wherein the split ratio is 100:1; hydrogen flow rate: 40ml/min; air flow rate: 350ml/min; tail gas purge flow: 25ml/min.
Example 1
Preparing 1mL of rhodium chloride solution with the concentration of 2mol/L, adding 20mmol of ethylenediamine into the rhodium chloride solution, and stirring to obtain a solution 1; 40g of 40wt% tetrapropylammonium hydroxide solution is taken, 0.5g of potassium hydroxide, 42g of tetraethyl silicate and 100mL of water are added into the solution, and the solution 2 is obtained by stirring; mixing the solution 1 with the solution 2; stirring at 25 ℃ for 8h; then transferring to 250mL stainless steel autoclave with polytetrafluoroethylene lining, standing at 110deg.C for 24h, filtering, washing the solid with 30mL water three times, drying, roasting at 550deg.C for 6h in air atmosphere, and then at 10% H 2 /90％N 2 In the atmosphere, the mixture was reduced at 400℃for 4 hours to prepare a 0.15% Rh/MFI catalyst (Rh mass is 0.15% of the mass of the MFI molecular sieve support) designated as # 1. FIG. 1 is a HAADF-STEM diagram of example 1, obtained by FEI Titan 3 The images of Rh nanoparticles measured at 300kV voltage were measured by Themis 60-300, in which the majority of-1 nm Rh was encapsulated in the channels of the MFI molecular sieve.
Into the autoclave, 100mmol of 1-hexene as a reaction substrate, 200ml of toluene as a reaction solvent, and 2g of 0.15% Rh/MFI catalyst were placed in this order. CO is used for replacing air in the autoclave for multiple times, and after the replacement is finished, CO and H with the total pressure of 5Mpa and the volume ratio of 1:1 are filled in 2 . The reaction was carried out at 85℃for 6h, and the mixture was subjected to quantitative chromatography after the autoclave was cooled to room temperature. The reaction results of the catalyst for catalyzing the hydroformylation of olefins are shown in table 1.
Example 2
Preparing 1mL of cobalt nitrate solution with the concentration of 2mol/L, adding 20mmol of ethylenediamine into the solution, and stirring to obtain solution 3; solution 2 was prepared as in example 1; mixing the solution 3 with the solution 2; stirred at 25℃for 8h and then transferred to250mL stainless steel autoclave with polytetrafluoroethylene lining, at 110deg.C for 24h, filtering, washing the solid with 30mL water three times, drying, roasting in air atmosphere at 550deg.C for 6h, and then at 10% H 2 /90％N 2 In the atmosphere, the mixture was reduced at 400℃for 4 hours to prepare a 0.15% Co/MFI catalyst (Co mass is 0.15% of the mass of the MFI molecular sieve support), designated as # 2.
Into the autoclave, 100mmol of 1-hexene as a reaction substrate, 200ml of toluene as a reaction solvent, and 2g of 0.15% Co/MFI catalyst were placed in this order. CO is used for replacing air in the autoclave for multiple times, and after the replacement is finished, CO and H with the total pressure of 5Mpa and the volume ratio of 1:1 are filled in 2 . The mixture was reacted at 160℃for 18 hours, and after the autoclave was cooled to room temperature, the mixture was subjected to quantitative chromatography. The reaction results of the catalyst for catalyzing the hydroformylation of olefins are shown in table 1.
Example 3
Preparing 1mL of rhodium chloride solution with the concentration of 2mol/L, adding 20mmol of ethylenediamine into 1mL of ammonium hexachloroiridate solution with the concentration of 2mol/L, mixing, and stirring to obtain a solution 4; solution 2 was prepared as in example 1; mixing solution 4 with solution 2, stirring at 30deg.C for 8 hr, transferring to 250mL stainless steel autoclave with polytetrafluoroethylene lining, standing at 110deg.C for 24 hr, filtering, washing the solid with 30mL water three times, drying, calcining at 550deg.C for 6 hr in air atmosphere, and calcining at 10% H 2 /90％N 2 In the atmosphere, reducing for 4 hours at 400 ℃, and preparing 0.15 percent of Rh-0.15 percent of Ir/MFI catalyst (the mass of Rh accounts for 0.15 percent of the mass of the MFI molecular sieve carrier, the mass of Ir accounts for 0.15 percent of the mass of the MFI molecular sieve carrier), which is marked as No. 3. FIG. 2 is a HAADF-STEM diagram of example 3# 3; by FEI Titan 3 The images of Rh nanoparticles and Ir nanoparticles measured at 300kV voltage by Themis 60-300, in which the majority of-1 nm Rh and-1 nm Ir were encapsulated in the channels of the MFI molecular sieve.
Into an autoclave, 100mmol of 1-hexene as a reaction substrate, 200ml of toluene as a reaction solvent, and 2g of 0.15% Rh-0.15% Ir/MFI catalyst were placed in this order. CO is used for replacing air in the autoclave for multiple times, and after the replacement is finished, the total pressure is filled to 5Mpa, and the volume ratio is1:1 CO and H 2 . The reaction was carried out at 85℃for 6h, and the mixture was subjected to quantitative chromatography after the autoclave was cooled to room temperature. The reaction results of the catalyst for catalyzing the hydroformylation of olefins are shown in table 1.
Example 4
Preparing 1mL of rhodium chloride solution with the concentration of 2mol/L, adding 20mmol of ethylenediamine into 1mL of ammonium tetrachloroaurate solution with the concentration of 2mol/L, mixing, and stirring to obtain a solution 5; solution 2 was prepared as in example 1; mixing solution 5 with solution 2, stirring at 30deg.C for 8 hr, transferring to 250mL stainless steel autoclave with polytetrafluoroethylene lining, standing at 110deg.C for 24 hr, filtering, washing the solid with 30mL water three times, drying, calcining at 550deg.C for 6 hr in air atmosphere, and calcining at 10% H 2 /90％N 2 And (3) in the atmosphere, reducing at 400 ℃ for 4 hours to prepare 0.15 percent of Rh-0.15 percent of Au/MFI catalyst (the mass of Rh accounts for 0.15 percent of the mass of the MFI molecular sieve carrier, and the mass of Au accounts for 0.15 percent of the mass of the MFI molecular sieve carrier), wherein the mass is denoted as No. 4#. FIG. 3 is a HAADF-STEM diagram of example 4# 4. By FEI Titan 3 The images of Rh nanoparticles and Au nanoparticles measured at 300kV voltage of Themis 60-300, in this sample, most of-1 nm Rh and-1 nmAu were encapsulated in the channels of the MFI molecular sieve.
Into an autoclave, 100mmol of 1-hexene as a reaction substrate, 200ml of toluene as a reaction solvent, and 2g of 0.15% Rh-0.15% Au/MFI catalyst were placed in this order. CO is used for replacing air in the autoclave for multiple times, and after the replacement is finished, CO and H with the total pressure of 5Mpa and the volume ratio of 1:1 are filled in 2 . The reaction was carried out at 85℃for 6h, and the mixture was subjected to quantitative chromatography after the autoclave was cooled to room temperature. The reaction results of the catalyst for catalyzing the hydroformylation of olefins are shown in table 1.
Example 5
Solution 1 was prepared as in example 1; 39g of 40wt% tetrabutylammonium hydroxide solution was taken, 0.4g of potassium hydroxide, 42g of tetraethyl silicate and 13mL of water were added thereto, and the mixture was stirred to obtain a solution 6; mixing solution 1 and solution 6, stirring at 30deg.C for 12 hr, transferring to 250mL stainless steel autoclave with polytetrafluoroethylene lining, standing at 130deg.C for 30 hr, filtering, and washing the solid with 30mL water three timesDrying, calcining at 550deg.C for 8 hr in air atmosphere, and then calcining at 10% H 2 /90％N 2 In the atmosphere, the catalyst was reduced at 500℃for 4 hours to prepare a 0.15% Rh/MEL catalyst (Rh mass is 0.15% of the MEL molecular sieve support mass) designated as # 5.
Into the autoclave, 100mmol of 1-hexene as a reaction substrate, 200ml of toluene as a reaction solvent, and 2g of 0.15% Rh/MEL catalyst were placed in this order. CO is used for replacing air in the autoclave for multiple times, and after the replacement is finished, CO and H with the total pressure of 5Mpa and the volume ratio of 1:1 are filled in 2 . The reaction was carried out at 85℃for 6h, and the mixture was subjected to quantitative chromatography after the autoclave was cooled to room temperature. The reaction results of the catalyst for catalyzing the hydroformylation of olefins are shown in table 1.
Example 6
Solution 1 was prepared as in example 1; taking 16.2g of tetraethylammonium fluoride, adding 30g of water, stirring, then adding 0.5g of sodium hydroxide and 42g of tetraethyl silicate, stirring for 6 hours at 25 ℃, adding solution 1, and stirring for 2 hours; then transferring to 250mL stainless steel autoclave with polytetrafluoroethylene lining, standing at 140 ℃ for 48h, filtering, washing the solid with 30mL water three times, drying, roasting at 550 ℃ for 8h in air atmosphere, and then at 10% H 2 /90％N 2 In the atmosphere, the mixture was reduced at 500℃for 4 hours to prepare a catalyst of 0.15% Rh/. Times.BEA (mass of Rh is 0.15% of the mass of the BEA molecular sieve support), designated as # 6.
Into an autoclave, 100mmol of the reaction substrate 1-hexene, 200ml of toluene reaction solvent, and 2g of 0.15% rh/. Times.bea catalyst were placed in this order. CO is used for replacing air in the autoclave for multiple times, and after the replacement is finished, CO and H with the total pressure of 5Mpa and the volume ratio of 1:1 are filled in 2 . The reaction was carried out at 85℃for 6h, and the mixture was subjected to quantitative chromatography after the autoclave was cooled to room temperature. The reaction results of the catalyst for catalyzing the hydroformylation of olefins are shown in table 1.
Example 7
Solution 1 was prepared as in example 1; taking 28.8g of 1, 6-bis (N-methylpyrrolidine diammonium hydroxide) hexane, adding 120mL of water, stirring, then adding 42g of tetraethyl silicate, stirring at 30 ℃ for 24 hours, removing ethanol generated during the stirring, adding solution 1, and stirring again2h; then transferring to 250mL stainless steel autoclave with polytetrafluoroethylene lining, standing at 170deg.C for 300h, filtering, washing the solid with 30mL water three times, drying, roasting at 550deg.C for 8h in air atmosphere, and then at 10% H 2 /90％N 2 In the atmosphere, the catalyst was reduced at 500℃for 6 hours to prepare a catalyst of 0.15% Rh/-SVR (Rh mass is 0.15% of the mass of the support of the-SVR molecular sieve), designated as # 7.
Into the autoclave, 100mmol of 1-hexene as a reaction substrate, 200ml of toluene as a reaction solvent, and 2g of 0.15% Rh/-SVR catalyst were placed in this order. CO is used for replacing air in the autoclave for multiple times, and after the replacement is finished, CO and H with the total pressure of 5Mpa and the volume ratio of 1:1 are filled in 2 . The reaction was carried out at 85℃for 6h, and the mixture was subjected to quantitative chromatography after the autoclave was cooled to room temperature. The reaction results of the catalyst for catalyzing the hydroformylation of olefins are shown in table 1.
Example 8
Preparing 1mL of cobalt nitrate solution with the concentration of 2mol/L, adding 20mmol of ethylenediamine into 1mL of ammonium hexachloroiridate solution with the concentration of 2mol/L, mixing, and stirring to obtain a solution 7; taking 28.8g of 1, 6-bis (N-methylpyrrolidine diammonium hydroxide) hexane, adding 120mL of water, stirring, then adding 42g of tetraethyl silicate, stirring at 30 ℃ for 24 hours, removing ethanol generated during the stirring, adding solution 7, and stirring for 2 hours; then transferring to a 250mL stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, standing for 300h at 170 ℃, filtering, washing the solid with 30mL water for three times, drying, roasting at 550 ℃ for 8h in an air atmosphere, and then reducing at 500 ℃ for 6h to prepare the 0.15% Co-0.15% Ir/-SVR catalyst (Co mass accounts for 0.15% of the mass of the-SVR molecular sieve carrier, ir mass accounts for 0.15% of the mass of the-SVR molecular sieve carrier), and marking as No. 8#.
Into an autoclave, 100mmol of 1-hexene as a reaction substrate, 200ml of toluene as a reaction solvent, and 2g of 0.15% Co-0.15% Ir/-SVR catalyst were placed in this order. CO is used for replacing air in the autoclave for multiple times, and after the replacement is finished, CO and H with the total pressure of 5Mpa and the volume ratio of 1:1 are filled in 2 . The mixture was reacted at 160℃for 18 hours, and after the autoclave was cooled to room temperature, the mixture was subjected to quantitative chromatography. Catalyst for catalyzing hydroformylation of olefinsThe reaction results of (2) are shown in Table 1.
Example 9
The substrate under evaluation was replaced with 1-octene, otherwise as in example 1.
Example 10
The substrate under evaluation was replaced with 1-undecene, otherwise as in example 1.
Example 11
The substrate under evaluation was replaced with 1-pentadecene, otherwise as in example 1.
Example 12
The substrate to be evaluated was replaced with 2-hexene, and the procedure of example 1 was followed.
Example 13
The substrate under evaluation was replaced with 2-octene, otherwise as in example 1.
Comparative example 1
A rhodium chloride solution of 0.15wt% Rh was impregnated onto 20g of a silica support by impregnation, then dried, calcined in an air atmosphere at 550℃for 6 hours, then dried in 10% H 2 /90％N 2 Reducing for 4h at 400 ℃ in atmosphere to obtain 0.15 percent of Rh-SiO 2 Catalyst (Rh mass occupying SiO) 2 0.15% of the mass of the carrier).
Into an autoclave, 100mmol of 1-hexene as a reaction substrate, 200ml of toluene as a reaction solvent, and 2g of 0.15% Rh-SiO were placed in this order 2 A catalyst. CO is used for replacing air in the autoclave for multiple times, and after the replacement is finished, CO and H with the total pressure of 5Mpa and the volume ratio of 1:1 are filled in 2 . The reaction was carried out at 85℃for 6h, and the mixture was subjected to quantitative chromatography after the autoclave was cooled to room temperature. The reaction results of the catalyst for catalyzing the hydroformylation of olefins are shown in table 1.
Comparative example 2
40g of 40wt% tetrapropylammonium hydroxide solution was taken, 0.5g of potassium hydroxide, 42g of tetraethyl silicate, 100mL of water was added thereto, and stirred at 25℃for 8 hours; then transferring to 250mL stainless steel autoclave with polytetrafluoroethylene lining, standing at 110deg.C for 24h, filtering, washing the solid with 30mL water three times, drying, and roasting at 550deg.C for 6h in air atmosphere to obtain MFI carrier. By impregnation, 0.15wt%Rhodium trichloride solution of Rh was impregnated on 20g of MFI carrier, then dried, calcined again in an air atmosphere at 550℃for 6 hours, then calcined in 10% H 2 /90％N 2 In the atmosphere, the reaction was carried out at 400℃for 4 hours to obtain 0.15% of Rh-MFI catalyst (the mass of Rh was 0.15% of the mass of the carrier).
Into an autoclave, 100mmol of 1-hexene as a reaction substrate, 200ml of toluene as a reaction solvent, and 2g of 0.15% Rh-MFI catalyst were placed in this order. CO is used for replacing air in the autoclave for multiple times, and after the replacement is finished, CO and H with the total pressure of 5Mpa and the volume ratio of 1:1 are filled in 2 . The reaction was carried out at 85℃for 6h, and the mixture was subjected to quantitative chromatography after the autoclave was cooled to room temperature. The reaction results of the catalyst for catalyzing the hydroformylation of olefins are shown in table 1.
TABLE 1 reaction results of various catalysts for the hydroformylation of olefins
Figure BDA0004059572490000111
As shown in the table, the heterogeneous catalyst provided by the invention is suitable for the hydroformylation of the medium-long carbon chain olefins with the carbon number of C5-C20, has the characteristics of high catalytic activity, high selectivity, very high positive-to-negative ratio of products and the like, and has important industrial application value.
The present invention is not described in detail in part as being well known to those skilled in the art. The above examples are merely illustrative of preferred embodiments of the invention, which are not exhaustive of all details, nor are they intended to limit the invention to the particular embodiments disclosed. Various modifications and improvements of the technical scheme of the present invention will fall within the protection scope of the present invention as defined in the claims without departing from the design spirit of the present invention.

Claims (10)

1. A heterogeneous catalyst for catalyzing the hydroformylation of medium-long carbon chain olefins is characterized in that: the catalyst is a molecular sieve encapsulated sub-nanocluster catalyst and consists of a catalytic active component and a carrier, wherein the catalytic active component is one, two or more of metal Rh, co, ir and Au, and the carrier is a molecular sieve.
2. The heterogeneous catalyst of claim 1, wherein: the active components and the carrier are combined in a form of molecular sieve encapsulation active component sub-nanocluster; the mass of the active component element accounts for 0.01 to 1.0 percent of the mass of the carrier, and is preferably 0.1 to 0.5 percent; the average particle size of the active component sub-nanocluster is 0.5-1.2 nm.
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 molecular sieve carrier is a hydrophobic all-silicon molecular sieve;
preferably, the catalytic active component is metal Rh and Ir, more preferably the mass ratio of metal Rh to Ir is 0.1-10:1;
preferably, the catalytic active component is metal Rh and Au, more preferably the mass ratio of metal Rh to Au is 0.1-10:1;
preferably, the catalytically active component is a metal Co and Ir, more preferably the mass ratio of metal Co to Ir is from 0.1 to 10:1.
4. The method for preparing the catalyst as claimed in claim 1, comprising the steps of:
(1) Mixing water-soluble metal salt and organic amine to obtain a mixed solution a; preferably, the water-soluble metal salt is selected from one, two or more of a water-soluble rhodium salt, a water-soluble cobalt salt, a water-soluble iridium salt and a water-soluble gold salt;
(2) Mixing a molecular sieve template agent, a silicon source, optional alkali and water to obtain a mixed solution b;
mixing the mixed solution a and the mixed solution b, then treating for 10-300 h at the temperature of 80-170 ℃, filtering, washing and drying to obtain solid powder;
(3) And (3) roasting and reducing the solid powder obtained in the step (2) to obtain the molecular sieve encapsulated sub-nanocluster catalyst.
5. The method according to claim 4, wherein:
in the step (2), the molecular sieve template agent is one or more of tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide, and is used for synthesizing the molecular sieve with an MFI topological structure; or the molecular sieve template agent is one or more of 1, 8-octanediamine, tetrabutylammonium bromide, tetrabutylammonium fluoride, tetrabutylammonium hydroxide and tetrabutylphosphine hydroxide, and is used for synthesizing the molecular sieve with the MEL topological structure; or the molecular sieve template agent is one or more of tetraethylammonium bromide, tetraethylammonium fluoride and tetraethylammonium hydroxide, and is used for synthesizing the molecular sieve with the BEA topological structure; or the molecular sieve template agent is one or more of 1-methyl-1- [6- (trimethylammonium) hexyl ] -pyrrolidine ammonium difluoride, 1-methyl-1- [6- (trimethylammonium) hexyl ] -pyrrolidine ammonium dihydrogen oxide, 1, 6-bis (N-methylpyrrolidine ammonium difluoride) hexane and 1, 6-bis (N-methylpyrrolidine ammonium hydroxide) hexane, and is used for synthesizing the molecular sieve with a-SVR topological structure; preferably, the silicon source is one or more of tetramethyl orthosilicate, tetraethyl silicate, butyl orthosilicate and sodium silicate; preferably the base is one or more of ammonia, sodium hydroxide and potassium hydroxide.
6. The method according to claim 4, wherein: in the step (1), the water-soluble rhodium salt is one or more of rhodium trichloride, rhodium nitrate, rhodium sulfate and rhodium acetate, preferably rhodium trichloride;
the water-soluble cobalt salt is one or more of cobalt dichloride, cobalt trichloride, cobalt nitrate, cobalt acetate and cobalt 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, wherein: in the step (3), the roasting temperature is 450-750 ℃, the roasting time is 2-20 h, and the roasting atmosphere is air atmosphere; preferably, the reduction temperature is 400-700 ℃, the reduction time is 3-15H, and the reduction atmosphere H 2 And N 2 The mixing atmosphere, preferably the reducing atmosphere is 10% H 2 /90％N 2 Atmosphere.
8. Use of the heterogeneous catalyst according to any one of claims 1 to 3 or the heterogeneous catalyst prepared according to any one of claims 4 to 7 as a hydroformylation of medium-long carbon chain olefins of C5 to C20 for the preparation of aldehydes, characterized in that the medium-long carbon chain olefins comprise medium-long carbon chain alpha-olefins of C5 to C20 and internal olefins.
9. Use according to claim 8, characterized in that: the reaction temperature of the hydroformylation reaction is 60-180 ℃, the reaction pressure is 2-7.0 Mpa, and the reaction time is 2-24 h; preferred reaction solvents are one or more of toluene, anisole, para-xylene and tetrahydrofuran; preferred feed gases are CO and H 2 The volume ratio of (2) is 1:1-1:3.
10. Use according to claim 8, characterized in that: the reaction for preparing aldehyde by hydroformylation of long and medium carbon chain olefins uses a reaction kettle for intermittent production or uses a fixed bed and a fluidized bed for continuous production, and a linear aldehyde product with the positive-to-negative ratio of more than 20 is obtained.
CN202310053845.6A 2023-02-03 2023-02-03 Heterogeneous catalyst for catalyzing long and medium carbon chain olefin hydroformylation, preparation method and application thereof Pending CN115999616A (en)

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