A modified heterogeneous catalyst for propylene hydroformylation and its preparation method and application

Abstract

The application discloses a modified heterogeneous catalyst for preparing n-butyraldehyde through propylene hydroformylation and a preparation method and application thereof. The catalyst is composed of an active component, an auxiliary agent M, a carrier and a modified component, the active component is Rh, the auxiliary agent M is one or more of Ni, Cu and Ru, the carrier is a full-silica molecular sieve Silicate-2, and the modified component is an S-containing organic ligand. The active component and the auxiliary agent M are encapsulated in the molecular sieve Silicate-2 channel in the form of sub-nano cluster alloy, and the surface of the catalyst is modified by the S-containing organic ligand of the modified component. The modified heterogeneous catalyst is used in a catalytic propylene hydroformylation reaction, has high catalytic activity, selectivity and n-iso ratio of products, has excellent stability and reusability, the catalyst is easy to separate from reaction products, and has high industrial application value.

Description

Technical Field

[0001] This invention belongs to the field of hydroformylation reaction catalysts, specifically relating to a modified heterogeneous catalyst for the hydroformylation of propylene to prepare n-butyraldehyde, its preparation method, and its application. Background Technology

[0002] The hydroformylation of propylene to prepare n-butyraldehyde and isobutyraldehyde is one of the most important homogeneous catalytic reactions in the world. n-Butyraldehyde and isobutyraldehyde are raw materials for the production of important chemicals such as butanol, 2-ethylhexanol, and neopentyl glycol, with a global annual production capacity of approximately seven million tons. To date, propylene hydroformylation remains dominated by Rh-based homogeneous complexation catalytic processes.

[0003] Homogeneous catalytic systems for propylene hydroformylation possess advantages such as uniform concentration distribution, high reactivity and selectivity, and good heat transfer, making them the mainstream industrial technology for olefin hydroformylation. Currently, they are broadly classified into three types: high-pressure, medium-pressure, and low-pressure methods. Among these, the low-pressure rhodium synthesis technology has the widest application, with relatively mature technologies including Davy's, Mitsubishi Chemical, and BASF. However, because the catalyst and reactants are in the same phase, catalyst separation is difficult, resulting in high recovery costs. Considering these factors, attention has shifted to heterogeneous catalytic systems. The advantage of these systems is that the catalyst and reactants are in different phases, making catalyst separation relatively easy and facilitating catalyst recovery and regeneration. This reduces catalyst loss and cost, contributing to a more economical and efficient catalytic reaction process.

[0004] To address the challenges of homogeneous reactions, the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences collaborated with China National Chemical Engineering Co., Ltd. (CNCEC Shanghai) to develop a supported heterogeneous hydroformylation system. This system was applied in an industrial plant for the production of n-propanol from ethylene (Contemporary Petroleum & Petrochemical, 2023, 31: 29-34). The catalyst used was a single-atom catalyst for the heterogeneous hydroformylation of olefins, independently developed by the research team of Ding Yunjie at DICP. However, the synthesis of the ligands used in this catalyst was relatively complex. The research team of Zeng Jie (Nature Communications, 2016, 7: 14036-14044) prepared a Rh / CoO single-atom catalyst by supporting rhodium on a cobalt oxide support, with a rhodium content of 0.2 wt%. When applied to the hydroformylation reaction of propylene, a TOF of 2065 h⁻¹ was achieved. -1Meanwhile, the selectivity of straight-chain aldehydes is as high as 94.4%, but the stability is unsatisfactory. Patent CN107537481A discloses the preparation of a Rh-based single-atom supported catalyst. The main active component of this catalyst is rhodium, and the support is nano-zinc oxide. The rhodium content is about 0.005-2.0 wt% of the catalyst. This catalyst can achieve a single-pass conversion number of tens of thousands in the propylene hydroformylation reaction, but it lacks regioselectivity. Patent CN 104475161A discloses a method for preparing a hydroformylation catalyst with rhodium complexes immobilized by ferromagnetic nanoparticles. This catalyst has good catalytic activity in the propylene hydroformylation reaction and solves the problem of recovering metallic rhodium in industry by using an external magnetic field. However, this catalyst still uses sensitive phosphine ligands and has low selectivity.

[0005] To address the problems of low activity and low selectivity exhibited in existing propylene hydroformylation heterogeneous catalysts, the inventors innovatively encapsulated the noble metal Rh and the promoter M in the pores of the molecular sieve Silicate-2 in the form of sub-nano cluster alloys, and modified the catalyst surface using S-containing organic ligands. This not only ensures that the catalyst has high activity and stability, but also significantly improves the selectivity of the catalyst for linear aldehydes. Summary of the Invention

[0006] To address the aforementioned technical problems, the present invention aims to provide a modified heterogeneous catalyst for the hydroformylation of propylene to prepare n-butyraldehyde, its preparation method, and its application. The modified heterogeneous catalyst of the present invention exhibits high catalytic activity, selectivity, and a high n-to-iso ratio in the catalytic hydroformylation reaction. Furthermore, it possesses excellent stability and reusability, and the catalyst is easily separated from the reaction products, thus demonstrating high industrial application value.

[0007] Specifically, the present invention is achieved through the following technical solutions:

[0008] In a first aspect, the present invention provides a modified heterogeneous catalyst for the hydroformylation of propylene to prepare n-butyraldehyde, the catalyst comprising an active component, an auxiliary agent M, a support, and a modifying component, wherein the active component is Rh, the auxiliary agent M is one or more of Ni, Cu, and Ru, the support is an all-silica molecular sieve Silicate-2, and the modifying component is an S-containing organic ligand, wherein the active component and the auxiliary agent M are encapsulated in the pores of the molecular sieve Silicate-2 in the form of a sub-nano cluster alloy, and the surface of the catalyst is modified by the S-containing organic ligand of the modifying component.

[0009] Preferably, in the above-mentioned modified heterogeneous catalyst, the mass of the Rh element accounts for 0.05 to 0.6 wt.% of the mass of the molecular sieve support, the mass of the auxiliary agent M accounts for 0.01 to 0.2 wt.% of the mass of the molecular sieve support, and the molar ratio of the modified component containing the S organic ligand to the Rh element is 0.01 to 10:1.

[0010] Preferably, in the above-mentioned modified heterogeneous catalyst, the S-containing organic ligand of the modified component is selected from one or more of the following S-containing organic ligands L1, L2, L3, L4, and L5, which have different degrees of coordination characteristics with noble metal Rh:

[0011]

[0012] In a second aspect, the present invention provides a method for preparing the above-mentioned modified heterogeneous catalyst, comprising the following steps:

[0013] (1) In a hydrothermal reactor, the molecular sieve template agent, silicon source, alkali and water are mixed according to a certain metering and stirred at a temperature of 25-50℃ for 8-24 hours.

[0014] (2) Add soluble precious metal Rh salt, soluble auxiliary agent M salt and organic amine to the hydrothermal reactor of step (1) according to the metering, and then treat at 100℃~150℃ for 15~48h, centrifuge, wash and dry to obtain solid powder;

[0015] (3) The solid powder obtained in step (2) is calcined and reduced to obtain a molecular sieve-encapsulated sub-nano cluster catalyst;

[0016] (4) Take the S-containing organic ligands according to the metric amount and mix them with the molecular sieve encapsulated sub-nano cluster catalyst obtained in step (3). In a N2 protective atmosphere, treat the mixture at a temperature of 60-130℃ for 5-10 hours to obtain the S-containing organic ligand modified molecular sieve encapsulated sub-nano cluster catalyst.

[0017] In step (1) above, the molecular sieve template agent is selected from one or more of tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, and tetrabutylammonium hydroxide, preferably tetrabutylammonium hydroxide; the silicon source is selected from one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, and sodium silicate, preferably tetraethyl orthosilicate; and the alkali is selected from one or more of ammonia, sodium hydroxide, and potassium hydroxide, preferably potassium hydroxide.

[0018] In step (2) above, the soluble noble metal Rh salt is selected from one or more of rhodium trichloride, rhodium nitrate, rhodium sulfate, and rhodium acetate, preferably rhodium trichloride; the soluble auxiliary agent M salt is selected from one or more of nickel nitrate, nickel chloride, nickel acetate, copper nitrate, copper chloride, copper acetate, ruthenium nitrate, ruthenium chloride, and ruthenium acetate, preferably nickel nitrate, copper chloride, or ruthenium chloride; and the organic amine is selected from one or more of ethylenediamine, cyclohexylamine, and 1,4-butanediamine, preferably ethylenediamine.

[0019] In step (3) above, the calcination temperature is 450-650℃, the calcination time is 4-20h, the calcination atmosphere is air, the reduction temperature is 300-700℃, the reduction time is 3-15h, and the reduction atmosphere is 10% H2 / 90% N2 atmosphere.

[0020] In a third aspect, the present invention provides the application of the above-described modified heterogeneous catalyst or the modified heterogeneous catalyst prepared by the above method, wherein the modified heterogeneous catalyst is used to catalyze the hydroformylation reaction of propylene to prepare n-butyraldehyde.

[0021] In a fourth aspect, the present invention provides a method for preparing n-butyraldehyde by hydroformylation of propylene, comprising the following steps: mixing a modified heterogeneous catalyst of the first aspect or a modified heterogeneous catalyst prepared by the method of the second aspect, propylene, syngas, a solvent, and an S-containing organic ligand; and carrying out a propylene hydroformylation reaction at a temperature of 50–150°C and a pressure of 2–10 MPa for a reaction time of 1–10 h. The molar ratio of propylene to CO in the syngas is 1:15–40, the molar ratio of CO to H2 in the syngas is 1:1–5, the molar ratio of propylene to Rh element in the modified heterogeneous catalyst is 500–10000:1, and the molar ratio of the S-containing organic ligand added in the hydroformylation reaction to the Rh element in the modified heterogeneous catalyst is 0.05–10:1.

[0022] The method for preparing n-butyraldehyde by propylene hydroformylation according to the present invention uses an S-containing organic ligand added in the propylene hydroformylation reaction. This S-containing organic ligand is the same as the S-containing organic ligand in the modified heterogeneous catalyst, and is selected from one or more of the following S-containing organic ligands L1, L2, L3, L4, and L5, which have different degrees of coordination characteristics with noble metal Rh:

[0023]

[0024]

[0025] The method for preparing n-butyraldehyde by propylene hydroformylation according to the present invention uses a solvent selected from one or more of toluene, ethylbenzene, cyclohexane, acetonitrile, and p-xylene in the propylene hydroformylation reaction.

[0026] The method for preparing n-butyraldehyde by propylene hydroformylation according to the present invention uses a reaction vessel for batch production or a fixed bed or fluidized bed for continuous production.

[0027] Compared with the prior art, the present invention has the following advantages:

[0028] (1) The modified heterogeneous catalyst provided by the present invention modifies the catalyst surface by using S-containing organic ligands as the modifying component. After the S-containing organic ligands complex with the noble metal clusters on the catalyst surface, the raw materials can only undergo catalytic reaction when they enter the Silicate-2 pores of the molecular sieve. Thus, by utilizing the spatial confinement effect of the Silicate-2 pores of the molecular sieve, shape selectivity of the reaction products is achieved, significantly improving the selectivity of n-butyraldehyde, and thus obtaining a very high n-to-iso ratio of the product.

[0029] (2) The modified heterogeneous catalyst provided by the present invention utilizes the Silicate-2 molecular sieve encapsulation technology of noble metal active components and additive M to obtain sub-nanometer-sized active component particles, thereby significantly increasing the active centers on the active components and making the catalyst have high catalytic activity.

[0030] (3) The modified heterogeneous catalyst provided by the present invention uses metal promoter M to modify the active component Rh. Metal bonds will be formed between promoter M and Rh, realizing electronic modulation and spatial dispersion of active component Rh, thereby helping to improve the activity of the catalyst and the modulation of product distribution.

[0031] (4) The modified heterogeneous catalyst provided by the present invention not only has the metal bond formed between the promoter M and Rh to inhibit the loss of active component Rh, but also the special pore structure of molecular sieve Silicate-2 has the anchoring and confinement effect on Rh, which can also enhance the stability of Rh, thereby giving the catalyst excellent stability and reusability, and has high industrial application value.

[0032] (5) In the method for preparing n-butyraldehyde by hydroformylation of propylene provided by the present invention, adding an S-containing organic ligand in the hydroformylation reaction can compensate for the drawback of ligand detachment of modified heterogeneous catalyst during the reaction process, thereby giving the catalyst excellent stability and reusability.

[0033] (6) The modified heterogeneous catalyst and hydroformylation method provided by the present invention have the characteristics of strong operability and good economy. Detailed Implementation

[0034] The embodiments of the present invention are described in detail below. The embodiments are provided to better illustrate the content of the present invention and are only used to explain the present invention, and should not be construed as limiting the present invention.

[0035] Where specific techniques or conditions are not specified in the examples, they shall be applied in accordance with the techniques or conditions described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels.

[0036] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available products.

[0037] In this invention's embodiments, the product analysis method employs Agilent chromatography. The specific detection methods for n-aldehydes and iso-aldehydes are as follows:

[0038] Injection volume: 0.5 μL; Column temperature: 30℃ for 6 min, increase to 100℃ at 5℃ / min and hold for 2 min, increase to 220℃ at 10℃ / min and hold for 2 min; Injector temperature: 270℃; Detector temperature: 270℃.

[0039] Septum purge gas flow rate: 3 ml / min; column flow rate (N2): 1 ml / min; split injection, split ratio 50:1; hydrogen flow rate: 40 ml / min; air flow rate: 350 ml / min; tail gas purge flow rate: 25 ml / min.

[0040] Example 1

[0041] A method for preparing a 0.15 wt.% Rh-0.05 wt.% Ru / Silicate-2 catalyst modified with S-organic ligand L1 includes the following steps:

[0042] (1) 6.20 g tetrapropylammonium hydroxide, 4.12 g tetraethyl orthosilicate, 15.0 mg potassium hydroxide, and 1.00 g water were mixed in a hydrothermal reactor according to the measured amount and stirred at 35 °C for 12 h. Then, 4.6 mg rhodium trichloride, 1.2 mg ruthenium chloride, and 50.0 mg ethylenediamine were added to the above hydrothermal reactor and allowed to stand at 120 °C for 24 h. After centrifugation and washing, the resulting sample powder was dried at 110 °C for 12 h. Then, it was calcined at 500 °C for 8 h in an air atmosphere. Finally, it was reduced at 600 °C for 3 h in a 10% H2 / 90% N2 atmosphere to obtain molecular sieve encapsulated sub-nano clusters, namely 0.15 wt.% Rh-0.05 wt.% Ru / Silicate-2 catalyst.

[0043] (2) Take 0.05 g of 0.15 wt.% Rh-0.05 wt.% Ru / Silicate-2 catalyst and mix it with 1.0 ml of S-containing organic ligand L1. In a N2 protective atmosphere, treat it at 80 °C for 6 h to obtain a molecular sieve encapsulated sub-nano cluster catalyst modified with S-containing organic ligand L1, namely, 0.15 wt.% Rh-0.05 wt.% Ru / Silicate-2 catalyst modified with S-containing organic ligand L1.

[0044] The propylene hydroformylation reaction using the catalyst prepared above was carried out as follows: 12 ml of toluene reaction solvent, 6 μL of S-containing organic ligand L1, and 0.02 g of 0.15 wt.% Rh-0.05 wt.% Ru / Silicate-2 catalyst modified with S-containing organic ligand L1 were sequentially added to an autoclave. The air in the autoclave was replaced with CO several times. After replacement, a propylene / CO / H2 mixed gas with a total pressure of 4 MPa and a volume ratio of 1:4:16 was introduced. The reaction was carried out at 95 °C for 3 h. After the autoclave was cooled to room temperature, the mixture was subjected to chromatographic quantitative analysis. The results of the propylene hydroformylation reaction catalyzed by the catalyst prepared above are shown in Table 1.

[0045] Example 2

[0046] A method for preparing a 0.25 wt.% Rh-0.1 wt.% Ru / Silicate-2 catalyst modified with S-organic ligand L2 includes the following steps:

[0047] (1) 4.80 g tetrapropylammonium hydroxide, 4.12 g tetraethyl orthosilicate, 30.0 mg potassium hydroxide, and 2.00 g water were mixed in a hydrothermal reactor according to the measured amount and stirred at 45 °C for 10 h. Then, 7.7 mg rhodium trichloride, 2.4 mg ruthenium chloride, and 50.0 mg ethylenediamine were added to the above hydrothermal reactor and allowed to stand at 130 °C for 15 h. After centrifugation and washing, the resulting sample powder was dried at 110 °C for 12 h. Then, it was calcined at 550 °C for 6 h in an air atmosphere. Finally, it was reduced at 550 °C for 3 h in a 10% H2 / 90% N2 atmosphere to obtain molecular sieve encapsulated sub-nano clusters, namely 0.25 wt.% Rh-0.1 wt.% Ru / Silicate-2 catalyst.

[0048] (2) Take 0.05g of 0.25wt.%Rh-0.1wt.%Ru / Silicate-2 catalyst and mix it with 1.0ml of S-containing organic ligand L2. In a N2 protective atmosphere, treat it at 90℃ for 8h to obtain molecular sieve encapsulated sub-nano cluster catalyst modified with S-containing organic ligand L2, namely 0.25wt.%Rh-0.1wt.%Ru / Silicate-2 catalyst modified with S-containing organic ligand L2.

[0049] The propylene hydroformylation reaction using the catalyst prepared above was carried out as follows: 12 ml of cyclohexane reaction solvent, 5 μL of S-containing organic ligand L2, and 0.02 g of 0.25 wt.% Rh-0.1 wt.% Ru / Silicate-2 catalyst modified with S-containing organic ligand L2 were sequentially added to an autoclave. The air in the autoclave was replaced with CO several times. After replacement, a propylene / CO / H2 mixed gas with a total pressure of 5 MPa and a volume ratio of 1:4:16 was introduced. The reaction was carried out at 90 °C for 8 h. After the autoclave was cooled to room temperature, the mixture was subjected to chromatographic quantitative analysis. The results of the propylene hydroformylation reaction catalyzed by the catalyst prepared above are shown in Table 1.

[0050] Example 3

[0051] A method for preparing a 0.3 wt.% Rh-0.1 wt.% Ru-0.1 wt.% Ni / Silicate-2 catalyst modified with S-containing organic ligands L2 and L3 includes the following steps:

[0052] (1) 3.60 g tetrapropylammonium hydroxide, 4.12 g tetraethyl orthosilicate, 0.0 mg potassium hydroxide, and 2.00 g water were mixed in a hydrothermal reactor according to the measured amount and stirred at 40 °C for 15 h. Then, 9.2 mg rhodium trichloride, 2.4 mg ruthenium chloride, 5.9 mg nickel nitrate, and 50.0 mg ethylenediamine were added to the above hydrothermal reactor and allowed to stand at 135 °C for 10 h. After centrifugation and washing, the resulting sample powder was dried at 110 °C for 12 h. Then, it was calcined at 580 °C for 5 h in an air atmosphere. Finally, it was reduced at 500 °C for 12 h in a 10% H2 / 90% N2 atmosphere to obtain molecular sieve encapsulated sub-nano clusters, namely 0.3 wt.% Rh-0.1 wt.% Ru-0.1 wt.% Ni / Silicate-2 catalyst.

[0053] (2) Take 0.05g of 0.3wt.%Rh-0.1wt.%Ru-0.1wt.%Ni / Silicate-2 catalyst, mix it with 0.5ml of S-containing organic ligand L2 and 0.5ml of S-containing organic ligand L3, and treat it at 100℃ for 5h in N2 protective atmosphere to obtain molecular sieve encapsulated sub-nano cluster catalyst modified with S-containing organic ligands L2 and L3, namely 0.3wt.%Rh-0.1wt.%Ru-0.1wt.%Ni / Silicate-2 catalyst modified with S-containing organic ligands L2 and L3.

[0054] The propylene hydroformylation reaction using the catalyst prepared above was carried out as follows: 12 ml of ethylbenzene reaction solvent, 5 μL of S-containing organic ligand L2, 3 μL of S-containing organic ligand L3, and 0.02 g of 0.3 wt.% Rh-0.1 wt.% Ru-0.1 wt.% Ni / Silicate-2 catalyst modified with S-containing organic ligands L2 and L3 were sequentially added to an autoclave. The air in the autoclave was replaced with CO several times. After replacement, a propylene / CO / H2 mixed gas with a total pressure of 4 MPa and a volume ratio of 1:4:16 was introduced. The reaction was carried out at 100 °C for 4 h. After the autoclave was cooled to room temperature, the mixture was subjected to chromatographic quantitative analysis. The results of the propylene hydroformylation reaction catalyzed by the catalyst prepared above are shown in Table 1.

[0055] Example 4

[0056] A method for preparing a 0.18 wt.% Rh-0.1 wt.% Ni / Silicate-2 catalyst modified with S-containing organic ligands L1 and L4 includes the following steps:

[0057] (1) 6.20 g tetrapropylammonium hydroxide, 4.12 g tetraethyl orthosilicate, 40.0 mg potassium hydroxide, and 3.00 g water were mixed in a hydrothermal reactor according to the measured amount and stirred at 35 °C for 12 h. Then, 5.5 mg rhodium trichloride, 5.9 mg nickel nitrate, and 50.0 mg ethylenediamine were added to the above hydrothermal reactor and allowed to stand at 130 °C for 10 h. After centrifugation and washing, the resulting sample powder was dried at 110 °C for 12 h. Then, it was calcined at 560 °C for 8 h in an air atmosphere. Finally, it was reduced at 550 °C for 5 h in a 10% H2 / 90% N2 atmosphere to obtain molecular sieve encapsulated sub-nano clusters, namely 0.18 wt.% Rh-0.1 wt.% Ni / Silicate-2 catalyst.

[0058] (2) Take 0.05g of 0.18wt.%Rh-0.1wt.%Ni / Silicate-2 catalyst and mix it with 0.5ml of S-containing organic ligand L1 and 0.5ml of S-containing organic ligand L4. In a N2 protective atmosphere, treat it at 90℃ for 10h to obtain molecular sieve encapsulated sub-nano cluster catalyst modified with S-containing organic ligands L1 and L4, namely 0.18wt.%Rh-0.1wt.%Ni / Silicate-2 catalyst modified with S-containing organic ligands L1 and L4.

[0059] The propylene hydroformylation reaction using the catalyst prepared above was carried out as follows: 6 ml of toluene reaction solvent, 6 ml of acetonitrile reaction solvent, 4 μL of S-containing organic ligand L1, 4 μL of S-containing organic ligand L4, and 0.02 g of 0.18 wt.% Rh-0.1 wt.% Ni / Silicate-2 catalyst modified with S-containing organic ligands L1 and L4 were sequentially added to an autoclave. The air in the autoclave was replaced with CO several times. After replacement, a propylene / CO / H2 mixed gas with a total pressure of 6 MPa and a volume ratio of 1:4:16 was introduced. The reaction was carried out at 90 °C for 5 h. After the autoclave cooled to room temperature, the mixture was subjected to chromatographic quantitative analysis. The results of the propylene hydroformylation reaction catalyzed by the catalyst prepared above are shown in Table 1.

[0060] Example 5

[0061] A method for preparing a 0.3 wt.% Rh-0.25 wt.% Ni / Silicate-2 catalyst modified with S-containing organic ligands L2 and L5 includes the following steps:

[0062] (1) 8.60 g tetrapropylammonium hydroxide, 4.12 g tetraethyl orthosilicate, 60.0 mg potassium hydroxide, and 0.00 g water were mixed in a hydrothermal reactor according to the measured amount and stirred at 35 °C for 12 h. Then, 9.2 mg rhodium trichloride, 14.8 mg nickel nitrate, and 100.0 mg ethylenediamine were added to the above hydrothermal reactor and allowed to stand at 140 °C for 8 h. After centrifugation and washing, the resulting sample powder was dried at 110 °C for 12 h. Then, it was calcined at 550 °C for 6 h in an air atmosphere. Finally, it was reduced at 500 °C for 3 h in a 10% H2 / 90% N2 atmosphere to obtain molecular sieve encapsulated sub-nano clusters, namely 0.3 wt.% Rh-0.25 wt.% Ni / Silicate-2 catalyst.

[0063] (2) Take 0.05g of 0.3wt.%Rh-0.25wt.%Ni / Silicate-2 catalyst, mix it with 0.5ml of S-containing organic ligand L2 and 0.5ml of S-containing organic ligand L5, and treat it at 110℃ for 6h in N2 protective atmosphere to obtain molecular sieve encapsulated sub-nano cluster catalyst modified with S-containing organic ligands L2 and L5, namely 0.3wt.%Rh-0.25wt.%Ni / Silicate-2 catalyst modified with S-containing organic ligands L2 and L5.

[0064] The propylene hydroformylation reaction using the catalyst prepared above was carried out as follows: 12 ml of acetonitrile reaction solvent, 3 μL of S-containing organic ligand L2, 3 μL of S-containing organic ligand L5, and 0.02 g of 0.3 wt.% Rh-0.25 wt.% Ni / Silicate-2 catalyst modified with S-containing organic ligands L2 and L5 were sequentially added to an autoclave. The air in the autoclave was replaced with CO several times. After replacement, a propylene / CO / H2 mixed gas with a total pressure of 4 MPa and a volume ratio of 1:4:16 was introduced. The reaction was carried out at 85 °C for 8 h. After the autoclave cooled to room temperature, the mixture was subjected to chromatographic quantitative analysis. The results of the propylene hydroformylation reaction catalyzed by the catalyst prepared above are shown in Table 1.

[0065] Example 6

[0066] A method for preparing a 0.28 wt.% Rh-0.15 wt.% Ni-0.05 wt.% Cu / Silicate-2 catalyst modified with S-containing organic ligands L3 and L4 includes the following steps:

[0067] (1) 4.80 g tetrapropylammonium hydroxide, 4.12 g tetraethyl orthosilicate, 10.0 mg potassium hydroxide, and 2.00 g water were mixed in a hydrothermal reactor according to the measured amount and stirred at 35 °C for 12 h. Then, 8.6 mg rhodium trichloride, 8.9 mg nickel nitrate, 1.6 mg copper chloride, and 100.0 mg ethylenediamine were added to the above hydrothermal reactor and allowed to stand at 130 °C for 10 h. After centrifugation and washing, the resulting sample powder was dried at 110 °C for 12 h. Then, it was calcined at 500 °C for 10 h in an air atmosphere. Finally, it was reduced at 560 °C for 5 h in a 10% H2 / 90% N2 atmosphere to obtain molecular sieve encapsulated sub-nano clusters, namely 0.28 wt.% Rh-0.15 wt.% Ni-0.05 wt.% Cu / Silicate-2 catalyst.

[0068] (2) Take 0.05g of 0.28wt.%Rh-0.15wt.%Ni-0.05wt.%Cu / Silicate-2 catalyst, mix it with 0.5ml of S-containing organic ligand L3 and 0.5ml of S-containing organic ligand L4, and treat it at 100℃ for 8h in N2 protective atmosphere to obtain molecular sieve encapsulated sub-nano cluster catalyst modified with S-containing organic ligands L3 and L4, namely 0.28wt.%Rh-0.15wt.%Ni-0.05wt.%Cu / Silicate-2 catalyst modified with S-containing organic ligands L3 and L4.

[0069] The propylene hydroformylation reaction using the catalyst prepared above was carried out as follows: 6 ml of acetonitrile reaction solvent, 6 ml of toluene reaction solvent, 3 μL of sulfur-containing organic ligand L3, 3 μL of sulfur-containing organic ligand L4, and 0.02 g of 0.28 wt.% Rh-0.15 wt.% Ni-0.05 wt.% Cu / Silicate-2 catalyst modified with sulfur-containing organic ligands L3 and L4 were sequentially added to an autoclave. The air in the autoclave was replaced with CO several times. After replacement, a propylene / CO / H2 mixed gas with a total pressure of 4.5 MPa and a volume ratio of 1:4:16 was introduced. The reaction was carried out at 100 °C for 5 h. After the autoclave cooled to room temperature, the mixture was subjected to chromatographic quantitative analysis. The results of the propylene hydroformylation reaction catalyzed by the catalyst prepared above are shown in Table 1.

[0070] Example 7

[0071] A method for preparing a 0.15 wt.% Rh-0.08 wt.% Cu / Silicate-2 catalyst modified with S-organic ligand L2 includes the following steps:

[0072] (1) 6.20 g tetrapropylammonium hydroxide, 4.12 g tetraethyl orthosilicate, 40.0 mg potassium hydroxide, and 4.00 g water were mixed in a hydrothermal reactor according to the measured amount and stirred at 45 °C for 8 h. Then, 4.6 mg rhodium trichloride, 2.6 mg copper chloride, and 50.0 mg ethylenediamine were added to the above hydrothermal reactor and allowed to stand at 125 °C for 12 h. After centrifugation and washing, the resulting sample powder was dried at 110 °C for 12 h. Then, it was calcined at 560 °C for 12 h in an air atmosphere. Finally, it was reduced at 600 °C for 3 h in a 10% H2 / 90% N2 atmosphere to obtain molecular sieve encapsulated sub-nano clusters, namely 0.15 wt.% Rh-0.08 wt.% Cu / Silicate-2 catalyst.

[0073] (2) Take 0.05g of 0.15wt.%Rh-0.08wt.%Cu / Silicate-2 catalyst and mix it with 0.5ml of S-containing organic ligand L2. In a N2 protective atmosphere, treat it at 90℃ for 8h to obtain molecular sieve encapsulated sub-nano cluster catalyst modified with S-containing organic ligand L2, namely 0.15wt.%Rh-0.08wt.%Cu / Silicate-2 catalyst modified with S-containing organic ligand L2.

[0074] The propylene hydroformylation reaction using the catalyst prepared above was carried out as follows: 12 ml of toluene reaction solvent, 4 μL of S-containing organic ligand L2, and 0.02 g of 0.15 wt.% Rh-0.08 wt.% Cu / Silicate-2 catalyst modified with S-containing organic ligand L2 were sequentially added to an autoclave. The air in the autoclave was replaced with CO several times. After replacement, a propylene / CO / H2 mixed gas with a total pressure of 4 MPa and a volume ratio of 1:4:16 was introduced. The reaction was carried out at 90 °C for 5 h. After the autoclave was cooled to room temperature, the mixture was subjected to chromatographic quantitative analysis. The results of the propylene hydroformylation reaction catalyzed by the catalyst prepared above are shown in Table 1.

[0075] Example 8

[0076] A method for preparing a 0.35 wt.% Rh-0.2 wt.% Cu / Silicate-2 catalyst modified with S-containing organic ligands L4 and L5 includes the following steps:

[0077] (1) 8.00 g tetrapropylammonium hydroxide, 4.12 g tetraethyl orthosilicate, 20.0 mg potassium hydroxide and 1.00 g water were mixed in a hydrothermal reactor according to the measured amount and stirred at 35 °C for 12 h. Then, 10.7 mg rhodium trichloride, 6.5 mg copper chloride and 100.0 mg ethylenediamine were added to the above hydrothermal reactor and allowed to stand at 120 °C for 24 h. After centrifugation and washing, the sample powder was dried at 110 °C for 12 h. Then, it was calcined at 500 °C for 8 h in an air atmosphere. Finally, it was reduced at 560 °C for 5 h in a 10% H2 / 90% N2 atmosphere to obtain molecular sieve encapsulated sub-nano clusters, namely 0.35 wt.% Rh-0.2 wt.% Cu / Silicate-2 catalyst.

[0078] (2) Take 0.05g of 0.28wt.%Rh-0.15wt.%Ni-0.05wt.%Cu / Silicate-2 catalyst, mix it with 0.5ml of S-containing organic ligand L4 and 0.5ml of S-containing organic ligand L5, and treat it at 100℃ for 10h in N2 protective atmosphere to obtain molecular sieve encapsulated sub-nano cluster catalyst modified with S-containing organic ligands L4 and L5, namely 0.35wt.%Rh-0.2wt.%Cu / Silicate-2 catalyst modified with S-containing organic ligands L4 and L5. The propylene hydroformylation reaction using the catalyst prepared above was carried out as follows: 6 ml of toluene reaction solvent, 6 ml of cyclohexane reaction solvent, 3 μL of sulfur-containing organic ligand L4, 3 μL of sulfur-containing organic ligand L5, and 0.02 g of 0.35 wt.% Rh-0.2 wt.% Cu / Silicate-2 catalyst modified with sulfur-containing organic ligands L4 and L5 were sequentially added to an autoclave. The air in the autoclave was replaced with CO several times. After replacement, a propylene / CO / H2 mixed gas with a total pressure of 5 MPa and a volume ratio of 1:4:16 was introduced. The reaction was carried out at 85 °C for 8 h. After the autoclave cooled to room temperature, the mixture was subjected to chromatographic quantitative analysis. The results of the propylene hydroformylation reaction catalyzed by the catalyst prepared above are shown in Table 1.

[0079] Comparative Example 1

[0080] The preparation method of 0.15wt.%Rh-0.05wt.%Ru / Silicate-2 catalyst includes the following steps:

[0081] According to the specified dosage, 6.20 g of tetrapropylammonium hydroxide, 4.12 g of tetraethyl orthosilicate, 15.0 mg of potassium hydroxide, and 1.00 g of water were mixed in a hydrothermal reactor and stirred at 35 °C for 12 h. Then, 4.6 mg of rhodium trichloride, 1.2 mg of ruthenium chloride, and 50.0 mg of ethylenediamine were added to the above hydrothermal reactor, and the mixture was allowed to stand at 120 °C for 24 h. After centrifugation and washing, the resulting sample powder was dried at 110 °C for 12 h. Then, it was calcined at 500 °C for 8 h in an air atmosphere. Finally, it was reduced at 600 °C for 3 h in a 10% H2 / 90% N2 atmosphere to obtain molecular sieve-encapsulated sub-nano clusters, namely 0.15 wt.% Rh-0.05 wt.% Ru / Silicate-2 catalyst.

[0082] The propylene hydroformylation reaction using the catalyst prepared above was carried out as follows: 12 ml of toluene reaction solvent and 0.02 g of 0.15 wt.% Rh-0.05 wt.% Ru / Silicate-2 catalyst were sequentially added to an autoclave; the air in the autoclave was replaced with CO several times; after replacement, a propylene / CO / H2 mixed gas with a total pressure of 4 MPa and a volume ratio of 1:4:16 was introduced; the reaction was carried out at 95 °C for 3 h; after the autoclave was cooled to room temperature, the mixture was subjected to chromatographic quantitative analysis. The results of the propylene hydroformylation reaction catalyzed by the catalyst prepared above are shown in Table 1.

[0083] Comparative Example 2

[0084] The preparation method of 0.15wt.%Rh-0.05wt.%Ru / Silicate-2 catalyst includes the following steps:

[0085] According to the specified dosage, 6.20 g of tetrapropylammonium hydroxide, 4.12 g of tetraethyl orthosilicate, 15.0 mg of potassium hydroxide, and 1.00 g of water were mixed in a hydrothermal reactor and stirred at 35 °C for 12 h. Then, 4.6 mg of rhodium trichloride, 1.2 mg of ruthenium chloride, and 50.0 mg of ethylenediamine were added to the above hydrothermal reactor, and the mixture was allowed to stand at 120 °C for 24 h. After centrifugation and washing, the resulting sample powder was dried at 110 °C for 12 h. Then, it was calcined at 500 °C for 8 h in an air atmosphere. Finally, it was reduced at 600 °C for 3 h in a 10% H2 / 90% N2 atmosphere to obtain molecular sieve-encapsulated sub-nano clusters, namely 0.15 wt.% Rh-0.05 wt.% Ru / Silicate-2 catalyst.

[0086] The propylene hydroformylation reaction using the catalyst prepared above was carried out as follows: 12 ml of toluene reaction solvent, 6 μL of S-containing organic ligand L1, and 0.02 g of 0.15 wt.% Rh-0.05 wt.% Ru / Silicate-2 catalyst were sequentially added to an autoclave. The air in the autoclave was replaced with CO several times. After replacement, a propylene / CO / H2 mixed gas with a total pressure of 4 MPa and a volume ratio of 1:4:16 was introduced. The reaction was carried out at 95 °C for 3 h. After the autoclave cooled to room temperature, the mixture was subjected to chromatographic quantitative analysis. The results of the propylene hydroformylation reaction catalyzed by the catalyst prepared above are shown in Table 1.

[0087] Table 1: Results of the propylene hydroformylation reaction catalyzed by the catalyst prepared in this invention

[0088]

[0089]

[0090]

[0091] As shown in Table 1, the modified heterogeneous catalyst described in this invention exhibits high catalytic activity, selectivity, and a high product-to-iso ratio in the hydroformylation reaction of propylene, thus possessing high industrial application value.

[0092] Obviously, the above embodiments are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make various modifications and variations to the present invention without departing from the spirit and scope of the invention. Therefore, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention also intends to include these modifications and variations.

Claims

1. A modified heterogeneous catalyst for the hydroformylation of propene to produce n-butyraldehyde, characterized in that, The catalyst is composed of an active component, an auxiliary agent M, a carrier and a modification component, the active component is Rh, the auxiliary agent M is one or more of Ni, Cu and Ru, the carrier is a full-silica molecular sieve Silicate-2, and the modification component is an S-containing organic ligand, wherein the active component and the auxiliary agent M are encapsulated in the molecular sieve Silicate-2 channel in the form of sub-nanometer cluster alloy, and the surface of the catalyst is modified by the S-containing organic ligand of the modification component; The mass of the Rh element accounts for 0.05-0.6 wt.% of the mass of the molecular sieve carrier, the mass of the auxiliary agent M accounts for 0.01-0.2 wt.% of the mass of the molecular sieve carrier, and the molar ratio of the S-containing organic ligand of the modification component to the Rh element is 0.01-10:1; the S-containing organic ligand of the modification component is selected from one or more of S-containing organic ligands L1, L2, L3, L4 and L5 having different degrees of coordination of noble metal Rh characteristics: 。 2. The process for the preparation of the modified heterogeneous catalyst according to claim 1, characterized in that, The method comprises the following steps: (1) mixing a molecular sieve template agent, a silicon source, a base and water according to a certain amount in a hydrothermal kettle, stirring at a temperature of 25-50 ℃, and stirring for 8-24 h; (2) adding soluble noble metal Rh salt, soluble auxiliary agent M salt and organic amine into the hydrothermal kettle of step (1) according to the amount, then treating at a temperature of 100-150 ℃ for 15-48 h, centrifuging, washing, drying to obtain a solid powder; (3) calcining and reducing the solid powder obtained in step (2) to obtain a molecular sieve encapsulated sub-nanometer cluster catalyst; (4) taking the S-containing organic ligand according to the amount, mixing with the molecular sieve encapsulated sub-nanometer cluster catalyst obtained in step (3), treating at a temperature of 60-130 ℃ for 5-10 h in a N2 protective atmosphere to obtain a molecular sieve encapsulated sub-nanometer cluster catalyst modified by the S-containing organic ligand.

3. The process for the preparation of a modified heterogeneous catalyst according to claim 2, characterized in that, In step (1), the molecular sieve template agent is selected from one or more of tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide, the silicon source is selected from one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, butyl orthosilicate and sodium silicate, and the base is selected from one or more of ammonia, sodium hydroxide and potassium hydroxide; In step (2), the soluble noble metal Rh salt is selected from one or more of rhodium chloride, rhodium nitrate, rhodium sulfate and rhodium acetate, the soluble auxiliary agent M salt is selected from one or more of nickel nitrate, nickel chloride, nickel acetate, copper nitrate, copper chloride, copper acetate, ruthenium nitrate, ruthenium chloride and ruthenium acetate, and the organic amine is selected from one or more of ethylenediamine, cyclohexylamine and 1,4-butanediamine; In step (3), the calcination temperature is 450-650 ℃, the calcination time is 4-20 h, the calcination atmosphere is an air atmosphere, the reduction temperature is 300-700 ℃, the reduction time is 3-15 h, and the reduction atmosphere is a 10% H2 / 90% N2 atmosphere.

4. The process for the preparation of a modified heterogeneous catalyst according to claim 3, characterized in that, In step (1), the molecular sieve template agent is tetrabutylammonium hydroxide, the silicon source is tetraethyl orthosilicate, and the base is potassium hydroxide. In step (2), the soluble noble metal Rh salt is selected from rhodium trichloride, the soluble auxiliary M salt is selected from nickel nitrate or copper chloride or ruthenium chloride, and the organic amine is selected from ethylenediamine.

5. Use of the modified heterogeneous catalyst of claim 1 or the modified heterogeneous catalyst produced by the process of any one of claims 2-4, characterized in that, The modified heterogeneous catalyst is used to catalyze the propylene hydroformylation reaction to prepare n-butyraldehyde.

6. A process for the hydroformylation of propene to produce n-butyraldehyde, characterized in that, The method comprises the following steps: mixing the modified heterogeneous catalyst according to claim 1 or the modified heterogeneous catalyst prepared by the method according to any one of claims 2-4, propylene, synthesis gas, a solvent and an S-containing organic ligand, and performing the propylene hydroformylation reaction at a temperature of 50-150 ℃ and a pressure of 2-10 MPa for 1-10 h; wherein the molar ratio of propylene to CO in the synthesis gas is 1:15-40, the molar ratio of CO to H2 in the synthesis gas is 1:1-5, the molar ratio of propylene to Rh in the modified heterogeneous catalyst is 500-10000:1, and the molar ratio of the S-containing organic ligand added in the hydroformylation reaction to Rh in the modified heterogeneous catalyst is 0.05-10:1; the S-containing organic ligand added in the propylene hydroformylation reaction is the same as the modified component S-containing organic ligand in the modified heterogeneous catalyst, and is selected from one or more of the following S-containing organic ligands L1, L2, L3, L4 and L5 having different degrees of coordination noble metal Rh characteristics: 。 7. The process for the hydroformylation of propene to produce n-butyraldehyde according to claim 6, characterized in that, The solvent used in the propylene hydroformylation reaction is selected from one or more of toluene, ethylbenzene, cyclohexane, acetonitrile and p-xylene.

8. The process for the hydroformylation of propylene to produce n-butyraldehyde according to claim 6, characterized in that, The propylene hydroformylation reaction is produced in a batch mode using a reaction kettle or in a continuous mode using a fixed bed or a fluidized bed.

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