Heterogeneous catalysts, processes for their preparation and use thereof

Abstract

The application discloses a heterogeneous catalyst, a preparation method thereof, hydrogenated nitrile rubber, a preparation method and application thereof. The heterogeneous catalyst comprises a composite oxide carrier of SiO2 and group IVB metal oxide, and an active component Pd and oxides thereof loaded on the composite oxide carrier, wherein the group IVB metal oxide is TiO2 and / or ZrO2; surface characteristics of the composite oxide carrier are that infrared spectra exist three characteristic peaks at 620-710 cm ‑1 -1, and three characteristic peaks at 2850-2960 cm ‑1 -1. The heterogeneous catalyst of the application is used in cooperation with homogeneous catalysts to hydrogenate and saturate high polymer materials at low temperature and pressure, and the hydrogenated high polymer, especially the nitrile rubber product, has high hydrogenation degree. Moreover, the heterogeneous catalyst of the application can be used repeatedly, and the catalyst is easy to separate and recover.

Description

Technical Field

[0001] This invention relates to a heterogeneous catalyst, its preparation method, and its application. Background Technology

[0002] Nitrile rubber (NBR) is a copolymer polymerized from acrylonitrile and butadiene monomers. It exhibits excellent oil resistance, high abrasion resistance, good heat resistance, and strong adhesion. Its disadvantages include poor low-temperature resistance, poor odor resistance, low insulation performance, and low elasticity. It is widely used in the manufacture of various oil-resistant rubber products in the automotive, aerospace, and petroleum industries.

[0003] Hydrogenated nitrile butadiene rubber (HNBR) is a product obtained by catalytic selective hydrogenation of the unsaturated olefin segments on the hydrocarbon chain of nitrile butadiene rubber (NBR). Hydrogenated nitrile butadiene rubber possesses excellent properties such as good oil resistance, heat resistance, chemical corrosion resistance, odor resistance, high tear resistance, and abrasion resistance.

[0004] Currently, the main method for industrial-scale HNBR production is solution hydrogenation, which includes homogeneous and heterogeneous hydrogenation. Homogeneous hydrogenation involves dispersing the catalyst active component in molecular form within a polymer solution, and then catalytically hydrogenating the polymer under specific reaction conditions. However, a common drawback of homogeneous solution hydrogenation is the difficulty in separating the catalyst from the product.

[0005] Heterogeneous catalytic reaction systems utilize supported noble metal catalysts. However, the preparation of supported catalysts currently relies on traditional impregnation methods, resulting in larger active component particle sizes and a significant reduction in the number of active sites. Furthermore, due to the weak interaction between the active component and the support, the noble metal is easily detached and lost from the support surface after vigorous stirring, reducing catalyst availability and affecting the performance of the hydrogenation products. Rion Corporation used SiO2 as a support to support Pd metal for the hydrogenation of nitrile rubber, achieving a single-pass hydrogenation degree of over 95%. However, the catalyst's performance deteriorated with repeated use, with a significant decrease in the degree of hydrogenation.

[0006] Therefore, it is necessary to develop a catalyst and related usage methods that can ensure a high degree of hydrogenation, easy separation and recovery of the catalyst, and multiple uses of heterogeneous catalysts. Summary of the Invention

[0007] To address the aforementioned problems in existing technologies, this invention provides a novel supported noble metal heterogeneous catalyst, wherein the surface characteristics of the composite oxide support are such that the infrared spectrum is in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1Three characteristic peaks are observed at the surface, indicating that this composite oxide support can significantly improve the dispersion of active components on the catalyst surface and control the active component atomic clusters to be no larger than 5 nm, thereby significantly improving the hydrogenation activity of the catalyst. Furthermore, the synergistic use of the heterogeneous catalyst and homogeneous catalyst of this invention not only ensures hydrogenation saturation of polymer materials at lower temperatures and pressures, resulting in hydrogenated polymers (especially hydrogenated nitrile rubber) with a high degree of hydrogenation, but also ensures the multiple uses of the heterogeneous catalyst and facilitates catalyst separation and recovery. More significantly, it avoids the loss of precious metal active components, further improving catalyst recyclability and reducing preparation costs.

[0008] The first aspect of this invention provides a heterogeneous catalyst, comprising: a composite oxide support of SiO2 and a group IVB metal oxide, and an active component Pd and its oxide supported on the composite oxide support, wherein the group IVB metal oxide is TiO2 and / or ZrO2; the surface characteristics of the composite oxide support are such that the infrared spectrum is in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 Three characteristic peaks are present. In this invention, the infrared spectroscopy measurement conditions were performed using a Nicolet iS50 infrared spectrometer, and the sample preparation and scanning were conducted in attenuated total reflectance mode, with a scanning range of 4000–4000 cm⁻¹. -1 The resolution is 4cm. -1 The number of scans was 32. For example... Figure 1 As shown, the surface properties of the composite oxide support of the present invention are as follows: infrared spectrum 620-710 cm⁻¹ -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 There are three characteristic peaks at this point.

[0009] According to some embodiments of the heterogeneous catalyst of the present invention, the composite oxide support is obtained by surface treatment of a composite support of SiO2 and group IVB metal oxides using an impregnation solution containing an organic cationic quaternary ammonium salt.

[0010] According to some embodiments of the heterogeneous catalyst of the present invention, the organic cationic quaternary ammonium salt is a long-chain alkyl quaternary ammonium salt with C6 or more chains; more preferably, the organic cationic quaternary ammonium salt is selected from dimethylbis(octadecyl)ammonium chloride, hexadecyltrimethylammonium chloride, and C6... 12-14 At least one of alkyl dimethyl ethyl benzyl ammonium chloride.

[0011] According to some embodiments of the heterogeneous catalyst of the present invention, the content of group IVB metal oxide is 5-25 wt% and the content of SiO2 is 75-95 wt% based on the total weight of the composite oxide support.

[0012] According to some embodiments of the heterogeneous catalyst of the present invention, the content of Pd and its oxides, calculated as Pd, is 0.5 to 2 wt% based on the total weight of the heterogeneous catalyst.

[0013] According to some embodiments of the heterogeneous catalyst of the present invention, the heterogeneous catalyst further includes Mo and its oxides supported on the support. The inventors surprisingly discovered that a composite oxide support of molybdenum-modified SiO2 and group IVB metal oxides, combined with impregnation of soluble Pd salts using an impregnation method, followed by drying and calcination, yields Pd-Mo / TiO2-SiO2. The modified support surface exhibits stronger Pd binding capacity, more uniform Pd dispersion, and improved hydrogenation activity on hydrogenated nitrile butadiene rubber, with high activity remaining even after repeated use.

[0014] According to some embodiments of the heterogeneous catalyst of the present invention, the content of Mo and its oxides, calculated as Mo, is 0.1 to 0.5 wt% based on the total weight of the heterogeneous catalyst. For example, but not limited to, 0.1 to 0.4 wt%, 0.1 to 0.3 wt%, 0.1 to 0.2 wt%, 0.2 to 0.5 wt%, 0.2 to 0.4 wt%, 0.2 to 0.3 wt%, 0.3 to 0.5 wt%, 0.3 to 0.4 wt%, 0.4 to 0.5 wt%, etc.

[0015] According to some embodiments of the heterogeneous catalyst of the present invention, the particle size of the heterogeneous catalyst is 5–30 μm. Examples, but not limited to, are 5–25 μm, 5–20 μm, 5–15 μm, 5–10 μm, 10–30 μm, 10–25 μm, 10–20 μm, 10–15 μm, 15–30 μm, 15–25 μm, 15–20 μm, 20–30 μm, and 20–25 μm. In this invention, the particle size of the catalyst is measured according to the test method NB / SH / T 0951-2017, using a Malvern MS2000 laser particle size analyzer.

[0016] According to some embodiments of the heterogeneous catalyst of the present invention, the average pore size of the heterogeneous catalyst is 100–1200 nm. Examples, but not limited to, are 100–1000 nm, 100–800 nm, 100–600 nm, 100–500 nm, 100–400 nm, 100–300 nm, 100–200 nm, 200–1200 nm, 200–1000 nm, 200–800 nm, 200–600 nm, 200–500 nm, 200–400 nm, 200–300 nm, 300–1200 nm, 300–1000 nm, 300–800 nm, 300–600 nm, 300–500 nm, 300–400 nm, and 400–1200 nm. 0nm, 400~1000nm, 400~800nm, 400~600nm, 400~500nm, 500~1200nm, 500~1000nm, 500~800nm, 500~600nm, 600~1200nm, 600~1000nm, 600~800nm, 600~700nm, 700~1200nm, 700~1000nm, 700~800nm, 800~1200nm, 800~1000nm, 900~1200nm, 900~1000nm, 1000~1200nm, etc. In this invention, the average pore size of the catalyst is measured according to the mercury porosimetry method for determining the pore size distribution and porosity of solid materials by the first part of GBT 21650.1-2008, which is a high-performance fully automatic mercury porosimetry instrument of the AutoPoreIV 9500 model from Micron Instruments, Inc.

[0017] According to some embodiments of the heterogeneous catalyst of the present invention, the specific surface area of ​​the heterogeneous catalyst is 30-200 m². 2 / g. For example, but not limited to, 30–150 mg. 2 / g, 30~120m 2 / g, 30~100m 2 / g, 30~80m 2 / g, 30~60m 2 / g, 30~50m 2 / g, 50~200m 2 / g, 50~150m 2 / g, 50~120m 2 / g, 50~100m 2 / g, 50~80m 2 / g, 50~60m 2 / g, 80~200m 2 / g, 80~150m 2 / g, 80~120m 2 / g, 80~100m 2 / g, 100~200m 2 / g, 100~150m 2 / g, 100~120m 2 / g, 120~200m 2 / g, 120~150m 2 / g etc. In this invention, the specific surface area of ​​the catalyst is measured according to the mercury porosimetry method for determining the pore size distribution and porosity of solid materials by the first part of GBT 21650.1-2008, using a high-performance fully automatic mercury porosimetry instrument, model AutoPoreIV 9500, manufactured by Micron Instruments, Inc.

[0018] A second aspect of this invention provides a method for preparing a heterogeneous catalyst, comprising the following steps:

[0019] (1) The SiO2 microsphere carrier is first impregnated with a solution containing group IVB metal compounds, then dried and calcined to obtain a composite carrier, wherein the group IVB metal compounds are titanium-containing compounds and / or zirconium-containing compounds.

[0020] (2) The composite carrier is surface-treated with an impregnation solution containing organic cationic quaternary ammonium salt to obtain a composite oxide carrier;

[0021] (3) The composite oxide carrier is second impregnated with a soluble salt of Pd, then dried and calcined.

[0022] According to some embodiments of the method for preparing heterogeneous catalysts according to the present invention, the impregnation solution containing organic cationic quaternary ammonium salt includes organic cationic quaternary ammonium salt, solvent, and acid.

[0023] In some embodiments of the method for preparing the heterogeneous catalyst according to the present invention, the organic cationic quaternary ammonium salt is a long-chain alkyl quaternary ammonium salt with C6 or more, more preferably selected from dimethyl dioctadecylammonium chloride, hexadecyltrimethylammonium chloride, and C6+. 12-14 At least one of alkyl dimethyl ethyl benzyl ammonium chloride.

[0024] In some embodiments of the method for preparing heterogeneous catalysts according to the present invention, the solvent is selected from at least one of deionized water, methanol, ethanol, acetone, butanone, tetrahydrofuran, o-xylene, and p-xylene.

[0025] In some embodiments of the method for preparing the heterogeneous catalyst according to the present invention, the acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, and citric acid. More preferably, the concentration of the acid is 1 to 98.3 wt%.

[0026] In some embodiments of the method for preparing the heterogeneous catalyst according to the present invention, the concentration of the quaternary ammonium salt solution in the impregnation solution containing the organic cationic quaternary ammonium salt is 0.1–10 wt%. More preferably, the weight ratio of the organic cationic quaternary ammonium salt, solvent, and acid is 1:10–19:1–3. For example, in the examples, 1 mL of 37 wt% concentrated hydrochloric acid weighs 1.18 g.

[0027] According to some embodiments of the method for preparing heterogeneous catalysts according to the present invention, the surface treatment is impregnation and drying. Preferably, the impregnation conditions include: a temperature of 20-60°C and a time of 0.5-8h; the drying conditions include: a temperature of 50-120°C and a time of 2-10h.

[0028] According to some embodiments of the preparation method of the heterogeneous catalyst of the present invention, the surface characteristics of the composite oxide after quaternary ammonium salt treatment are such that the infrared spectrum is in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 Three characteristic peaks are present. Infrared spectroscopy measurements can be performed using a Nicolet iS50 infrared spectrometer. Sample preparation and scanning were performed in attenuated total reflectance mode, with a scanning range of 4000–4000 cm⁻¹. -1， Resolution 4cm -1 The number of scans was 32.

[0029] In this invention, SiO2 microspheres can be simultaneously impregnated with a solution containing titanium compounds and / or zirconium compounds, followed by drying and calcination to obtain a composite oxide support of SiO2, TiO2, and / or ZrO2; alternatively, SiO2 microspheres can be first impregnated with a solution containing titanium compounds, then dried and calcined, followed by impregnation with a solution containing zirconium compounds, then drying and calcination, to obtain a composite oxide support of SiO2, TiO2, and / or ZrO2; furthermore, SiO2 microspheres can be first impregnated with a solution containing zirconium compounds, then dried and calcined, followed by impregnation with a solution containing titanium compounds, then drying and calcination, to obtain a composite oxide support of SiO2, TiO2, and / or ZrO2.

[0030] According to some embodiments of the preparation method of the heterogeneous catalyst of the present invention, after step (2) and before step (3), the preparation method further includes: dissolving a soluble salt of molybdenum and impregnating the surface-treated composite oxide support to obtain a Mo-modified surface-treated composite oxide support. The inventors were surprised to find that using the molybdenum-modified composite oxide support, combined with impregnation of a soluble salt of Pd, resulted in a stronger binding capacity of the modified support surface for Pd, more uniform Pd dispersion, and improved hydrogenation activity on hydrogenated nitrile rubber, with high activity even after repeated use.

[0031] According to some embodiments of the method for preparing heterogeneous catalysts according to the present invention, the soluble salt of Mo is selected from at least one of molybdenum trioxide, ammonium molybdate, and ammonium polymolybdate.

[0032] According to some embodiments of the preparation method of the heterogeneous catalyst of the present invention, the molar ratio of the soluble salt of molybdenum to SiO2 is 1:1500-2000, wherein the soluble salt of molybdenum is calculated as molybdenum element and SiO2 is calculated as Si.

[0033] In some embodiments of the method for preparing the heterogeneous catalyst according to the present invention, the solution used for dissolution is selected from at least one of ammonia, dilute acid solution, and alkaline solution. In the present invention, the dilute acid solution and alkaline solution are chosen to dissolve soluble salts of Mo, and will not be elaborated further here.

[0034] In some embodiments of the preparation method of the heterogeneous catalyst according to the present invention, the particle size of the SiO2 microsphere support is 5–30 μm. For example, but not limited to, 5–25 μm, 5–20 μm, 5–15 μm, 5–10 μm, 10–30 μm, 10–25 μm, 10–20 μm, 10–15 μm, 15–30 μm, 15–25 μm, 15–20 μm, 20–30 μm, 20–25 μm, etc. In this invention, the particle size of the SiO2 microsphere support is measured according to the test method NB / SH / T 0951-2017, using a Malvern MS2000 laser particle size analyzer.

[0035] In some embodiments of the preparation method of the heterogeneous catalyst according to the present invention, the average pore size of the SiO2 microsphere support is 100–1200 nm. Examples, but not limited to, are 100–1000 nm, 100–800 nm, 100–600 nm, 100–500 nm, 100–400 nm, 100–300 nm, 100–200 nm, 200–1200 nm, 200–1000 nm, 200–800 nm, 200–600 nm, 200–500 nm, 200–400 nm, 200–300 nm, 300–1200 nm, 300–1000 nm, 300–800 nm, 300–600 nm, 300–500 nm, 300–400 nm, 400–1200 nm. 0nm, 400~1000nm, 400~800nm, 400~600nm, 400~500nm, 500~1200nm, 500~1000nm, 500~800nm, 500~600nm, 600~1200nm, 600~1000nm, 600~800nm, 600~700nm, 700~1200nm, 700~1000nm, 700~800nm, 800~1200nm, 800~1000nm, 900~1200nm, 900~1000nm, 1000~1200nm, etc. In this invention, the average pore size of the SiO2 microsphere carrier is measured according to the mercury porosimetry method and gas adsorption method for determining the pore size distribution and porosity of solid materials, specifically the first part of GBT 21650.1-2008. The measurement is performed using a high-performance fully automated mercury porosimetry instrument, the AutoPoreIV 9500 model from Micron Instruments, Inc.

[0036] According to some embodiments of the preparation method of the supported catalyst of the present invention, the specific surface area of ​​the SiO2 microsphere support is 30-100 m². 2 / g. For example, but not limited to 30–100 mg. 2 / g, 30~90m 2 / g, 30~80m 2 / g, 30~70m 2 / g, 30~60m 2 / g, 30~50m 2 / g, 30~40m 2 / g, 50~100m 2 / g、

[0037] 50~90m 2 / g, 50~80m 2 / g, 50~70m 2 / g, 50~60m 2 / g, 80~100m 2 / g, 80~90m 2 / g etc. In this invention, the specific surface area of ​​the SiO2 microsphere carrier is measured according to the mercury porosimetry method and gas adsorption method for determining the pore size distribution and porosity of solid materials, specifically the first part of GBT 21650.1-2008. The measurement is performed using a high-performance fully automated mercury porosimetry instrument, model AutoPoreIV9500, manufactured by Micron Instruments, Inc.

[0038] In this invention, the silica microsphere carrier can be obtained commercially or in-house.

[0039] In some embodiments of the method for preparing the heterogeneous catalyst according to the present invention, the titanium-containing compound is selected from at least one of titanium sulfate, metatitanic acid, titanium tetrachloride, and tetrabutyl titanate. For example, metatitanic acid can be dissolved in a dilute sulfuric acid solution. As another example, tetrabutyl titanate can be dissolved in an ethanol solution.

[0040] In some embodiments of the method for preparing heterogeneous catalysts according to the present invention, the zirconium-containing compound is selected from at least one of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, and zirconium oxalate.

[0041] In some embodiments of the method for preparing heterogeneous catalysts according to the present invention, the soluble salt of Pd is selected from palladium sulfate, nitrate and halide, preferably at least one of palladium chloride, palladium nitrate, palladium acetate and palladium sulfate.

[0042] In some embodiments of the preparation method of the heterogeneous catalyst according to the present invention, the weight ratio of SiO2 microsphere support to titanium-containing compound and / or zirconium-containing compound is 7 to 20:1.

[0043] In some embodiments of the preparation method of the heterogeneous catalyst according to the present invention, the molar ratio of the composite oxide support to the soluble salt of Pd is 1:150 to 700.

[0044] According to some embodiments of the preparation method of the heterogeneous catalyst of the present invention, the conditions for the first impregnation include: a temperature of 20 to 60°C and a time of 0.5 to 8 hours.

[0045] According to some embodiments of the preparation method of the heterogeneous catalyst of the present invention, the conditions for the second impregnation include: a temperature of 20 to 60°C and a time of 0.5 to 8 hours.

[0046] According to some embodiments of the preparation method of the heterogeneous catalyst of the present invention, the conditions for the first drying include: a temperature of 105-130°C and a time of 2-8 hours.

[0047] According to some embodiments of the method for preparing heterogeneous catalysts according to the present invention, the conditions for the second drying include: a temperature of 105–1830°C and a time of 2–8 h.

[0048] According to some embodiments of the preparation method of the heterogeneous catalyst of the present invention, the conditions for the first calcination include: a temperature of 450-650°C and a time of 3-8 hours.

[0049] According to some embodiments of the preparation method of the heterogeneous catalyst of the present invention, the conditions for the second calcination include: a temperature of 450-650°C and a time of 3-8 hours.

[0050] According to some embodiments of the method for preparing heterogeneous catalysts according to the present invention, the amounts of SiO2 microsphere support and titanium-containing compound solution are such that, based on the total weight of the obtained composite oxide support of SiO2 and TiO2 and / or ZrO2, the content of TiO2 and / or ZrO2 is 5-25 wt%, and the content of SiO2 is 75-95 wt%.

[0051] In some embodiments of the preparation method of the heterogeneous catalyst according to the present invention, the amount of soluble salt of the second impregnation of Pd in ​​the composite oxide support of SiO2 and TiO2 and / or ZrO2 satisfies that the content of Pd and its oxide, calculated as Pd, is 0.5 to 2 wt% based on the total weight of the supported catalyst.

[0052] A third aspect of the present invention provides a heterogeneous catalyst obtained according to the above-described preparation method. It comprises: a composite oxide support of SiO2 and a group IVB metal oxide, and an active component Pd and its oxide supported on the composite oxide support, wherein the group IVB metal oxide is TiO2 and / or ZrO2; the surface characteristics of the composite oxide support are such that the infrared spectrum is in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 Three characteristic peaks are present. In this invention, the infrared spectroscopy measurement conditions were performed using a Nicolet iS50 infrared spectrometer, and the sample preparation and scanning were conducted in attenuated total reflectance mode, with a scanning range of 4000–4000 cm⁻¹. -1 The resolution is 4cm. -1 The number of scans was 32. For example... Figure 1 As shown, the surface properties of the composite oxide support of the present invention are as follows: infrared spectrum 620-710 cm⁻¹ -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 There are three characteristic peaks at this point.

[0053] According to some embodiments of the heterogeneous catalyst of the present invention, the composite oxide support is obtained by surface treatment of the composite support with an impregnation solution containing an organic cationic quaternary ammonium salt.

[0054] According to some embodiments of the heterogeneous catalyst of the present invention, the organic cationic quaternary ammonium salt is a long-chain alkyl quaternary ammonium salt with C6 or more chains; more preferably, the organic cationic quaternary ammonium salt is selected from dimethylbis(octadecyl)ammonium chloride, hexadecyltrimethylammonium chloride, and C6... 12-14 At least one of alkyl dimethyl ethyl benzyl ammonium chloride.

[0055] According to some embodiments of the heterogeneous catalyst of the present invention, the content of group IVB metal oxide is 5-25 wt% and the content of SiO2 is 75-95 wt% based on the total weight of the composite oxide support.

[0056] According to some embodiments of the heterogeneous catalyst of the present invention, the content of Pd and its oxides, calculated as Pd, is 0.5 to 2 wt% based on the total weight of the heterogeneous catalyst.

[0057] According to some embodiments of the heterogeneous catalyst of the present invention, the heterogeneous catalyst further includes Mo and its oxides supported on the support. The inventors surprisingly discovered that a composite oxide support of molybdenum-modified SiO2 and group IVB metal oxides, combined with impregnation of soluble Pd salts using an impregnation method, followed by drying and calcination, yields Pd-Mo / TiO2-SiO2. The modified support surface exhibits stronger Pd binding capacity, more uniform Pd dispersion, and improved hydrogenation activity on hydrogenated nitrile butadiene rubber, with high activity remaining even after repeated use.

[0058] According to some embodiments of the heterogeneous catalyst of the present invention, the content of Mo and its oxides, calculated as Mo, is 0.1 to 0.5 wt% based on the total weight of the heterogeneous catalyst. For example, but not limited to, 0.1 to 0.4 wt%, 0.1 to 0.3 wt%, 0.1 to 0.2 wt%, 0.2 to 0.5 wt%, 0.2 to 0.4 wt%, 0.2 to 0.3 wt%, 0.3 to 0.5 wt%, 0.3 to 0.4 wt%, 0.4 to 0.5 wt%, etc.

[0059] According to some embodiments of the heterogeneous catalyst of the present invention, the particle size of the heterogeneous catalyst is 5–30 μm. Examples, but not limited to, are 5–25 μm, 5–20 μm, 5–15 μm, 5–10 μm, 10–30 μm, 10–25 μm, 10–20 μm, 10–15 μm, 15–30 μm, 15–25 μm, 15–20 μm, 20–30 μm, and 20–25 μm. In this invention, the particle size of the catalyst is measured according to the test method NB / SH / T 0951-2017, using a Malvern MS2000 laser particle size analyzer.

[0060] According to some embodiments of the heterogeneous catalyst of the present invention, the average pore size of the heterogeneous catalyst is 100–1200 nm. Examples, but not limited to, are 100–1000 nm, 100–800 nm, 100–600 nm, 100–500 nm, 100–400 nm, 100–300 nm, 100–200 nm, 200–1200 nm, 200–1000 nm, 200–800 nm, 200–600 nm, 200–500 nm, 200–400 nm, 200–300 nm, 300–1200 nm, 300–1000 nm, 300–800 nm, 300–600 nm, 300–500 nm, 300–400 nm, and 400–1200 nm. 0nm, 400~1000nm, 400~800nm, 400~600nm, 400~500nm, 500~1200nm, 500~1000nm, 500~800nm, 500~600nm, 600~1200nm, 600~1000nm, 600~800nm, 600~700nm, 700~1200nm, 700~1000nm, 700~800nm, 800~1200nm, 800~1000nm, 900~1200nm, 900~1000nm, 1000~1200nm, etc. In this invention, the average pore size of the catalyst is measured according to the mercury porosimetry method for determining the pore size distribution and porosity of solid materials by the first part of GBT 21650.1-2008, which is a high-performance fully automatic mercury porosimetry instrument of the AutoPoreIV 9500 model from Micron Instruments, Inc.

[0061] According to some embodiments of the heterogeneous catalyst of the present invention, the specific surface area of ​​the heterogeneous catalyst is 30-200 m². 2 / g. For example, but not limited to, 30–150 mg. 2 / g, 30~120m 2 / g, 30~100m 2 / g, 30~80m 2 / g, 30~60m 2 / g, 30~50m 2 / g, 50~200m 2 / g, 50~150m 2 / g, 50~120m 2 / g, 50~100m 2 / g, 50~80m 2 / g, 50~60m 2 / g, 80~200m 2 / g, 80~150m 2 / g, 80~120m 2 / g, 80~100m 2 / g, 100~200m 2 / g, 100~150m 2 / g, 100~120m 2 / g, 120~200m 2 / g, 120~150m 2 / g etc. In this invention, the specific surface area of ​​the catalyst is measured according to the mercury porosimetry method for determining the pore size distribution and porosity of solid materials by the first part of GBT 21650.1-2008, using a high-performance fully automatic mercury porosimetry instrument, model AutoPoreIV 9500, manufactured by Micron Instruments, Inc.

[0062] A fourth aspect of the present invention provides a catalyst composition comprising a homogeneous catalyst and the above-described supported catalyst.

[0063] According to some embodiments of the catalyst composition of the present invention, homogeneous catalysts commonly used in the art can be used, such as transition metal ruthenium carbene complexes, Grubbs catalysts (e.g., catalysts for olefin metathesis), triphenylphosphine, and triphenylphosphine chlorides of platinum group metals. Preferably, the homogeneous catalyst comprises triphenylphosphine and triphenylphosphine chlorides of platinum group metals.

[0064] Specific transition metal ruthenium carbene complex catalysts include, but are not limited to, the structures of the following formulas (1) to (7):

[0065]

[0066]

[0067] The structure of Grubbs catalysts includes, but is not limited to, that shown in formula (8):

[0068]

[0069] In some embodiments of the hydrogenation method for hydrogenated nitrile butadiene rubber according to the present invention, the triphenylphosphine chloride of the platinum group metal is triphenylphosphine rhodium chloride and / or triphenylphosphine ruthenium chloride.

[0070] In some embodiments of the hydrogenation method for hydrogenated nitrile butadiene rubber according to the present invention, the weight ratio of triphenylphosphine to triphenylphosphine chloride of platinum group metals is 2 to 5:1. For example, but not limited to, 2 to 5:1, 2 to 4:1, 2 to 3:1, etc.

[0071] In some embodiments of the hydrogenation method for hydrogenated nitrile butadiene rubber according to the present invention, the weight ratio of the supported catalyst to the homogeneous catalyst is 1:0.01 to 0.3. For example, but not limited to, 1:0.05-0.3, 1:0.1-0.3, 1:0.15-0.3, 1:0.16-0.3, etc.

[0072] The fifth aspect of the present invention provides a method for hydrogenating a hydrogenated polymer, comprising: dissolving the polymer in an organic solvent, and then adding the above-mentioned catalyst composition to carry out a reaction.

[0073] In some embodiments of the preparation method of hydrogenated nitrile butadiene rubber according to the present invention, the polymer is nitrile butadiene rubber. In this art, nitrile butadiene rubber refers to a copolymer polymerized from acrylonitrile and butadiene monomers, and will not be elaborated further here.

[0074] In some embodiments of the preparation method of hydrogenated nitrile butadiene rubber according to the present invention, the organic solvent is selected from at least one of chlorobenzene, acetone, butanone, tetrahydrofuran, dichloromethane, chloroform, cyclohexanone, ethyl acetate and dimethylformamide.

[0075] In some embodiments of the method for preparing hydrogenated nitrile butadiene rubber according to the present invention, the heterogeneous catalyst is used in an amount of 5 to 20 wt% of the polymer.

[0076] According to some embodiments of the method for preparing hydrogenated nitrile butadiene rubber of the present invention, the reaction conditions include: a temperature of 30–90°C, a hydrogen pressure of 5–10 MPa, and a time of 5–10 h.

[0077] In some embodiments of the preparation method of hydrogenated nitrile butadiene rubber according to the present invention, the amount of organic solvent used to dissolve the polymer is such that the polymer content is 0.1-10 wt%. Examples include 0.1-10 wt%, 0.1-8 wt%, 0.1-6 wt%, 0.1-4 wt%, 0.1-2 wt%, 0.1-1 wt%, 0.5-10 wt%, 0.5-8 wt%, 0.5-6 wt%, 0.5-4 wt%, 0.5-2 wt%, 0.5-1 wt%, 1-10 wt%, 1-8 wt%, 1-6 wt%, 1-4 wt%, 1-2 wt%, 3-10 wt%, 3-8 wt%, 3-6 wt%, 3-4 wt%, 5-10 wt%, 5-8 wt%, 5-6 wt%, 7-10 wt%, 7-8 wt%, 8-10 wt%, and 9-10 wt%.

[0078] According to some embodiments of the method for preparing hydrogenated nitrile butadiene rubber according to the present invention, the method for preparing hydrogenated nitrile butadiene rubber may further include: after the reaction is completed, recovering the heterogeneous catalyst by filtration or centrifugation, and recovering the homogeneous catalyst by ion exchange with ion exchange resin.

[0079] The sixth aspect of the present invention provides a hydrogenated polymer obtained according to the preparation method described above, preferably, the hydrogenated polymer is hydrogenated nitrile rubber.

[0080] The seventh aspect of the present invention provides the above-described heterogeneous catalyst, the above-described preparation method, the above-described catalyst composition, the above-described hydrogenation method of the hydrogenated polymer, or the application of the above-described hydrogenated polymer in rubber products, especially in the field of hydrogenated nitrile rubber products.

[0081] The beneficial effects of this invention are:

[0082] (1) Modifying the composite oxide support of SiO2 and group IVB metal oxides with an impregnation solution containing organic cation quaternary ammonium salt can significantly improve the dispersion of active components on the catalyst surface and control the active component atomic clusters to be no larger than 5 nm, thereby significantly improving the hydrogenation activity of the catalyst.

[0083] (2) The supported catalyst prepared based on SiO2 composite oxide has a pore structure suitable for hydrogenation of macromolecules such as nitrile rubber. The TiO2 and / or ZrO2 on the support surface can improve the hydrogenation activity of the catalyst. The catalyst has good hydrogenation activity and stability.

[0084] (3) By combining the heterogeneous catalyst of the present invention with the homogeneous catalyst, hydrogen saturation of polymer materials is achieved at lower temperatures and pressures, and the resulting hydrogenated polymers (especially hydrogenated nitrile rubber products) have a high degree of hydrogenation.

[0085] (4) After the reaction is completed, the heterogeneous catalyst is recovered by filtration or centrifugation, and the homogeneous catalyst is recovered by ion exchange resin. This also ensures the multiple uses of the heterogeneous catalyst and makes the catalyst easy to separate and recover.

[0086] (5) The heterogeneous catalyst and the preparation method of hydrogenated nitrile rubber of the present invention, in a preferred case, use the noble metal palladium as the active component to prepare the supported heterogeneous catalyst of nitrile rubber, which further improves the recyclability of the catalyst and significantly reduces the cost of the catalyst, thereby reducing the production cost of hydrogenated polymers (especially hydrogenated nitrile rubber products). Attached Figure Description

[0087] Figure 1 The infrared spectrum of the composite oxide support provided in Embodiment 1 of the present invention.

[0088] Figure 2 The image shows the TEM characterization results of the heterogeneous catalyst A provided in Example 10 of this invention.

[0089] Figure 3 The infrared spectrum of the untreated TiO2-SiO2 composite support in Comparative Example 1 was obtained for testing.

[0090] Figure 4 Infrared spectra of the surface-treated SiO2 support for comparative example 5 were obtained for testing.

[0091] Figure 5 Comparison of infrared spectra of the carriers in Example 1, Comparative Example 1, and Comparative Example 5. Detailed Implementation

[0092] To make the present invention easier to understand, the present invention will be described in detail below with reference to embodiments. These embodiments are for illustrative purposes only and are not limited to the scope of application of the present invention.

[0093] In the following embodiments and comparative examples,

[0094] (1) The SiO2 microsphere carrier was purchased from Shandong Bangkai Materials Co., Ltd.

[0095] (2) Dimethyl dioctadecyl ammonium chloride, purchased from Beijing Bailingwei Technology Co., Ltd., CAS No. 61789-80-8.

[0096] (3) Hexadecyltrimethylammonium chloride, purchased from Beijing Bailingwei Technology Co., Ltd., CAS No. 112-02-7.

[0097] (4)C 12-14-Alkyl dimethyl ethyl benzyl ammonium chloride, purchased from Beijing Bailingwei Technology Co., Ltd., CAS No. 85409-23-0.

[0098] (5) In this invention, the content of Cu and its oxides, calculated as Cu, is obtained by ICP atomic emission spectrometry.

[0099] (6) The TiO2 content was determined using a spectrophotometer. The principle utilized is that in sulfuric acid solution, TiO2... 4+ It forms a yellow complex with hydrogen peroxide. Titanium dioxide reacts with hot sulfuric acid to form titanyl sulfate, which then reacts with hydrogen peroxide to form a stable, orange-yellow [TiO(H₂O₂)]₂. 2- The results were measured at 430 nm using a spectrophotometer.

[0100] (7) Similarly, the ZrO2 content was determined using a spectrophotometer.

[0101] (8) Infrared spectroscopy measurements were performed using a Nicolet iS50 infrared spectrometer. Sample preparation and scanning were performed in attenuated total reflectance mode. The scanning range was 4000–4000 cm⁻¹. -1 The resolution is 4cm. -1 The number of scans was 32.

[0102] (9) TEM characterization conditions: The catalyst was observed using a Jem-3010 high-resolution transmission electron microscope with an accelerating voltage of 200 kV for HR-TEM characterization. Before testing, the sample was thoroughly ground into powder. A small amount of sample was added to anhydrous ethanol and placed in an ultrasonic cleaner (model PS-10, Shenzhen Jiekang Ultrasonic Cleaning Machine Co., Ltd.) for ultrasonic separation for 15-20 min. Finally, the suspension was continuously added dropwise onto the microgrid using a dropper and allowed to air dry.

[0103] (10) The atomic cluster size of the active component copper was characterized by transmission electron microscopy (TEM) and measured according to the scale bar.

[0104]

Example 1

[0105] 85 g of SiO2 microspheres (particle size 20 μm, average pore size 110 nm) were impregnated with 420 mL of a 0.45 mol / L titanium sulfate solution at 25 °C for 6 h. The precipitate was then dried at 110 °C for 6 h and calcined at 550 °C for 5 h. A TiO2-SiO2 composite support with a TiO2 content of 15 wt% (SiO2 content 85 wt%) was obtained.

[0106] Take 5g of dimethylbis(octadecyl)ammonium chloride, add 95g of o-xylene, and mix evenly in 10mL of hydrochloric acid (37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at room temperature. After impregnation for 2h, dry at 60℃ for 12h to obtain the TiO2-SiO2 composite oxide support.

[0107] The prepared composite oxide support was characterized by infrared spectroscopy, and the infrared spectrum is shown below. Figure 1 The image shows the infrared spectrum of the surface-treated SiO2-TiO2 composite oxide. The infrared spectrum reveals that the surface characteristics of the composite oxide support in Example 1 are such that the infrared spectrum is in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 There are three characteristic peaks at this point.

[0108]

Example 2

[0109] The preparation method of the TiO2-SiO2 composite support is the same as in Example 1, except that 420 mL of a 0.45 mol / L titanium sulfate solution is replaced with 420 mL of a 0.75 mol / L dilute sulfuric acid solution of metatitanic acid, to obtain a TiO2-SiO2 composite support with a TiO2 content of 25 wt% (SiO2 content of 75 wt%).

[0110] Take 4g of dimethyl dioctadecyl ammonium chloride, add 96g of o-xylene, and mix evenly in 8mL of hydrochloric acid (37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite carrier at 20℃. After impregnation for 2h, dry at 60℃ for 12h to obtain the TiO2-SiO2 composite oxide carrier.

[0111] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1, with surface characteristics of infrared spectra in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 There are three characteristic peaks at this point.

[0112]

Example 3

[0113] The preparation method of the TiO2-SiO2 composite support is the same as in Example 1, except that 420 mL of a 0.45 mol / L titanium sulfate solution is replaced with 398 mL of a 0.38 mol / L titanium tetrachloride solution to obtain a TiO2-SiO2 composite support with a TiO2 content of 12 wt% (SiO2 content of 88 wt%).

[0114] Take 3g of hexadecyltrimethylammonium chloride, add 97g of o-xylene, and mix evenly in 7mL of hydrochloric acid (37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at 40℃. After impregnation for 2h, dry at 100℃ for 12h to obtain the TiO2-SiO2 composite oxide support.

[0115] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1, with surface characteristics of infrared spectra in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 There are three characteristic peaks at this point.

[0116]

Example 4

[0117] The preparation method of the TiO2-SiO2 composite support is the same as in Example 1, except that 420 mL of a 0.45 mol / L titanium sulfate solution is replaced with 360 mL of a 0.63 mol / L tetrabutyl titanate ethanol solution to obtain a TiO2-SiO2 composite support with a TiO2 content of 18 wt% (SiO2 content of 82 wt%).

[0118] Take 2g of C 12-14 1-alkyl dimethyl ethyl benzyl ammonium chloride, 98 g of o-xylene, and 5 mL of hydrochloric acid (37 wt%) were mixed evenly to prepare an impregnation solution. The TiO2-SiO2 composite oxide support was impregnated with the above impregnation solution at room temperature for 2 h and then dried at 60 °C for 12 h to obtain the TiO2-SiO2 composite oxide support.

[0119] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1, with surface characteristics of infrared spectra in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 There are three characteristic peaks at this point.

[0120]

Example 5

[0121] Following the method of Example 1, except that titanium sulfate was replaced with zirconium tetrachloride, a ZrO2-SiO2 composite support was finally obtained. A ZrO2-SiO2 composite support with a ZrO2 content of 15 wt% (SiO2 content of 85 wt%) was prepared.

[0122] Take 1g of dimethyl dioctadecyl ammonium chloride, add 99g of o-xylene, and mix evenly in 3mL of hydrochloric acid (37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the ZrO2-SiO2 composite carrier at 20℃. After impregnation for 2h, dry at 60℃ for 12h to obtain the ZrO2-SiO2 composite oxide carrier.

[0123] The infrared spectrum of the obtained ZrO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1, with surface characteristics of infrared spectra in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 There are three characteristic peaks at this point.

[0124]

Example 6

[0125] Take 85g of SiO2 microsphere carrier and impregnate it with 280mL of a 0.45mol / L titanium sulfate solution at 25℃ for 6h. Dry the precipitate at 110℃ for 6h and calcine it at 550℃ for 5h. Then impregnate it with 300mL of a 0.14mol / L zirconium nitrate solution at 25℃ for 4h. Dry the precipitate at 110℃ for 8h and calcine it at 550℃ for 6h.

[0126] A TiO2-ZrO2-SiO2 composite support with a TiO2 content of 10 wt% and a ZrO2 content of 5 wt% (SiO2 content of 85 wt%) was prepared.

[0127] Take 5g of dimethyl dioctadecyl ammonium chloride, add 95g of o-xylene, and mix evenly in 10mL of hydrochloric acid (37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-ZrO2-SiO2 composite support at room temperature for 2h, and then dry at 60℃ for 12h to obtain the TiO2-ZrO2-SiO2 composite oxide support.

[0128] The infrared spectrum of the obtained TiO2-ZrO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1, with surface characteristics of infrared spectra in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 There are three characteristic peaks at this point.

[0129]

Example 7

[0130] The preparation method of the TiO2-SiO2 composite oxide support is the same as in Example 1, except that the SiO2 microsphere support is replaced with a SiO2 microsphere support with a particle size of 10 μm and an average pore size of 200 nm.

[0131] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1, with surface characteristics of infrared spectra in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 There are three characteristic peaks at this point.

[0132]

Example 8

[0133] The preparation method of the TiO2-SiO2 composite oxide support is the same as in Example 1, except that the SiO2 microsphere support is replaced with a SiO2 microsphere support with a particle size of 5 μm and an average pore size of 120 nm.

[0134] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1, with surface characteristics of infrared spectra in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 There are three characteristic peaks at this point.

[0135]

Example 9

[0136] The preparation method of the TiO2-SiO2 composite oxide support is the same as in Example 1, except that the SiO2 microsphere support is replaced with a SiO2 microsphere support with a particle size of 30 μm and an average pore size of 1000 nm.

[0137] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1, with surface characteristics of infrared spectra in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 There are three characteristic peaks at this point.

[0138]

Example 10

[0139] 100g of the TiO2-SiO2 composite oxide support prepared in Examples 1-3 was added to 500mL of palladium chloride solution with a Pd content of 0.2-2.1g, impregnated for 180 minutes, dried at 110℃ for 6 hours, and then calcined at 500℃ for 4 hours to obtain Pd / TiO2-SiO2 catalyst (heterogeneous catalyst AC) with a Pd content of 0.2-2wt%. See Table 1 for details.

[0140] The heterogeneous catalyst A was characterized by TEM, and the results are shown in the figure. Figure 2 ,from Figure 2It can be seen that the active component Pd is uniformly dispersed, and the atomic cluster particle size of the active component is 2-5 nm, with an average atomic cluster particle size of 2.7 nm.

[0141]

Example 11

[0142] 100g of the TiO2-SiO2 composite oxide support prepared in Examples 1 and 4 were respectively immersed in 200mL of ammonia solution containing 0.10-0.51g of Mo in ammonium molybdate for 120 minutes, dried at 110℃ for 6 hours, and then calcined at 500℃ for 4 hours to obtain a support of 0.1-0.5wt% Mo-modified SiO2 and TiO2.

[0143] 100g of the Mo-modified SiO2 and TiO2 support prepared above was added to 500mL of palladium chloride solution with a Pd content of 0.5-2.1g, impregnated for 180 minutes, dried at 110℃ for 6 hours, and then calcined at 500℃ for 4 hours to obtain a Pd-Mo / TiO2-SiO2 catalyst (heterogeneous catalyst DG) with a Pd content of 0.5-2wt%. See Table 1 for details.

[0144]

Example 12

[0145] The method of Example 11 was followed, except that the TiO2-SiO2 composite oxide support prepared in Example 1 was replaced with the composite oxide supports prepared in Examples 5 and 6, respectively. The heterogeneous catalyst HI was obtained. Details are shown in Table 1.

[0146]

Example 13

[0147] 100g of the TiO2-SiO2 composite oxide support prepared in Example 1 was added to 200mL of an ammonia solution containing 0.51g of Mo in ammonium molybdate and impregnated for 120 minutes. It was then dried at 110°C for 6 hours and calcined at 600°C for 5 hours to obtain a support of 0.5wt% Mo-modified SiO2 and TiO2.

[0148] 100g of the Mo-modified SiO2 and TiO2 support prepared above were added to 500mL of palladium chloride solution with a Pd content of 2.1g, impregnated for 180 minutes, dried at 110℃ for 6 hours, and then calcined at 600℃ for 5 hours to obtain a Pd-Mo / TiO2-SiO2 catalyst (heterogeneous catalyst J) with a Pd content of 2wt%. See Table 1 for details.

[0149]

Example 14

[0150] 100g of the TiO2-SiO2 composite oxide support prepared in Example 1 was added to 200mL of an ammonia solution containing 0.51g of Mo in ammonium molybdate and impregnated for 120 minutes. It was then dried at 110°C for 6 hours and calcined at 650°C for 8 hours to obtain a support of 0.5wt% Mo-modified SiO2 and TiO2.

[0151] 100g of the Mo-modified SiO2 and TiO2 support prepared above was added to 500mL of palladium chloride solution with a Pd content of 2.1g, impregnated for 180 minutes, dried at 110℃ for 6 hours, and then calcined at 650℃ for 8 hours to obtain a Pd-Mo / TiO2-SiO2 catalyst (heterogeneous catalyst K) with a Pd content of 2wt%. See Table 1 for details.

[0152]

Example 15

[0153] The method of Example 11 was followed, except that the TiO2-SiO2 composite oxide support prepared in Example 1 was replaced with the composite oxide supports prepared in Examples 7-9. Heterogeneous catalysts L, M, and N were obtained. See Table 1 for details.

[0154] Table 1

[0155]

[0156] The particle size, average pore size, and specific surface area of ​​the heterogeneous catalyst AN were tested, and the results are shown in Table 2.

[0157] Particle size was determined according to the test method in NB / SH / T 0951-2017, using a Malvern MS2000 laser particle size analyzer.

[0158] The average pore size and specific surface area were determined according to the first part of GB / T 21650.1-2008, the mercury porosimetry method for determining the average pore size distribution and porosity of solid materials by mercury porosimetry and gas adsorption method. The high-performance fully automatic mercury porosimetry instrument, AutoPore IV 9500, manufactured by Micron Instruments, Inc., was used.

[0159] Table 2

[0160]

[0161]

Test Example 1

[0162] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of heterogeneous catalyst A, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.0g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 6MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0163] The hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (degree of unsaturation) according to the test method SH / T1762-2008 / ISO 14558:2000. The results showed that the degree of hydrogenation was 95.7%.

[0164] The selectivity of the obtained hydrogenated nitrile butadiene rubber was tested using infrared spectroscopy. The instrument used was a Nicolet 560 Fourier transform infrared spectrometer manufactured by Nicolet Corporation, USA. The results showed that the absorption peak intensity of -CN in the spectrum did not decrease after hydrogenation, and no absorption peak representing -NH2 appeared. This indicates that -CN did not change before and after the reaction, meaning that -CN was not hydrogenated, and the selectivity was 100%. The results showed that the selectivity was 100%.

[0165]

Test Example 2

[0166] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of heterogeneous catalyst A, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.0g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0167] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 96.2% and the selectivity was 100%.

[0168]

Test Example 3

[0169] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of heterogeneous catalyst B, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.0g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0170] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 96.0% and the selectivity was 100%.

[0171]

Test Example 4

[0172] Take 2L of 3wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of heterogeneous catalyst C, 0.5g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.2g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0173] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 95.3% and the selectivity was 100%.

[0174]

Test Example 5

[0175] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of heterogeneous catalyst D, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.0g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0176] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 97.6% and the selectivity was 100%.

[0177]

Test Example 6

[0178] After the reaction in Test Example 5 was completed, the heterogeneous catalyst D was centrifuged and recovered. It was then washed in the organic solvent chlorobenzene with stirring for 4 hours and centrifuged again. Under the same reaction conditions as in Test Example 5, it was added back to the reaction system to investigate its NBR supported catalytic performance. The experiment was repeated three times. The results of the degree of hydrogenation (according to the method in Test Example 1) and selectivity (NMR determination: obtained by comparing the CN group content in the feed and hydrogenated product) are listed in Table 3.

[0179] Table 3

[0180] Reuse once Reuse twice Reuse 3 times Hydrogenation degree 93.1％ 91.5％ 90.4％ Selective 100％ 100％ 100％

[0181]

Test Example 7

[0182] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of heterogeneous catalyst E, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.0g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 8MPa, and reaction time 5h; hydrogenated nitrile rubber is obtained.

[0183] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 97.3% and the selectivity was 100%.

[0184]

Test Example 8

[0185] Following the method of Test Example 1, except that heterogeneous catalyst A was replaced with heterogeneous catalyst F, and hydrogenated nitrile rubber was finally obtained.

[0186] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 97.9% and the selectivity was 100%.

[0187]

Test Example 9

[0188] Following the method of Test Example 1, except that heterogeneous catalyst A was replaced with heterogeneous catalyst G, and hydrogenated nitrile rubber was finally obtained.

[0189] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 93.6% and the selectivity was 100%.

[0190]

Test Example 10

[0191] Following the method of Test Example 1, except that heterogeneous catalyst A was replaced with heterogeneous catalyst H, and hydrogenated nitrile rubber was finally obtained.

[0192] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 93.2% and the selectivity was 100%.

[0193]

Test Example 11

[0194] Following the method of Test Example 1, except that heterogeneous catalyst A was replaced with heterogeneous catalyst I, and hydrogenated nitrile rubber was finally obtained.

[0195] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 98.1% and the selectivity was 100%.

[0196]

Test Example 12

[0197] Following the method of Test Example 1, except that heterogeneous catalyst A was replaced with heterogeneous catalyst J, and hydrogenated nitrile rubber was finally obtained.

[0198] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 98.0% and the selectivity was 100%.

[0199]

Test Example 13

[0200] Following the method of Test Example 1, except that heterogeneous catalyst A was replaced with heterogeneous catalyst K, and hydrogenated nitrile rubber was finally obtained.

[0201] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 98.1% and the selectivity was 100%.

[0202]

Test Example 14

[0203] The method is the same as in Test Example 1, except that the reaction conditions are: temperature 80℃, hydrogen pressure 6MPa, and reaction time 8h.

[0204] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 93.2% and the selectivity was 100%.

[0205]

Test Example 15

[0206] The method is the same as in Test Example 1, except that the reaction conditions are: temperature 70℃, hydrogen pressure 6MPa, and reaction time 8h.

[0207] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 91.3% and the selectivity was 100%.

[0208]

Test Example 16

[0209] The method is the same as in Test Example 1, except that the reaction conditions are: temperature 60℃, hydrogen pressure 6MPa, and reaction time 8h.

[0210] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (degree of unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 89.3% and the selectivity was 100%.

[0211]

Test Example 17

[0212] The method is the same as in Test Example 1, except that the reaction conditions are: temperature 50℃, hydrogen pressure 6MPa, and reaction time 8h.

[0213] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 88.6% and the selectivity was 100%.

[0214]

Test Example 18

[0215] Following the method of Test Example 1, except that heterogeneous catalyst A was replaced with heterogeneous catalyst L, and hydrogenated nitrile rubber was finally obtained.

[0216] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 95.6% and the selectivity was 100%.

[0217]

Test Example 19

[0218] Following the method of Test Example 1, except that heterogeneous catalyst A was replaced with heterogeneous catalyst M, and hydrogenated nitrile rubber was finally obtained.

[0219] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 95.3% and the selectivity was 100%.

[0220]

Test Example 20

[0221] Following the method of Test Example 1, except that heterogeneous catalyst A was replaced with heterogeneous catalyst N, and hydrogenated nitrile rubber was finally obtained.

[0222] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 96.4% and the selectivity was 100%.

[0223]

Test Example 21

[0224] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of heterogeneous catalyst D, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.2g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 6MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0225] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 97.7% and the selectivity was 100%.

[0226]

Test Example 22

[0227] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of heterogeneous catalyst D, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.6g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 6MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0228] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (degree of unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 97.8% and the selectivity was 100%.

[0229]

Test Example 23

[0230] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of heterogeneous catalyst D, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 2g of triphenylphosphine, and carry out a catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 6MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0231] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 97.7% and the selectivity was 100%.

[0232]

Test Example 24

[0233] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 12g of heterogeneous catalyst D, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.6g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 6MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0234] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (degree of unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 99.1% and the selectivity was 100%.

[0235]

Test Example 25

[0236] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of heterogeneous catalyst A, 0.5g of homogeneous catalyst triphenylphosphine ruthenium chloride, and 1.2g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 6MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0237] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 95.1% and the selectivity was 100%.

[0238]

Test Example 26

[0239] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of supported catalyst D, 0.08g of homogeneous catalyst triphenylphosphine rhodium chloride, and 0.40g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 95℃, hydrogen pressure 8MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0240] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 91.5% and the selectivity was 100%.

[0241] [Test Comparison Example 1]

[0242] The infrared spectrum of the untreated TiO2-SiO2 composite oxide support from Example 1 is shown below. Figure 3 The image shown is the infrared spectrum of the untreated TiO2-SiO2 composite support.

[0243] Then, the active component was loaded according to the method of Example 10, and finally a Pd / TiO2-SiO2 catalyst with a Pd content of 2wt% was obtained.

[0244] Following the method in Test Example 1, hydrogenated nitrile butadiene rubber was finally obtained.

[0245] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 86.8% and the selectivity was 99%.

[0246] [Test Comparison Example 2]

[0247] Using the TiO2-SiO2 composite oxide support from Example 1, and following the method of Example 8, except that Pd was replaced with Rh, a Rh / ZrO2-SiO2 catalyst (heterogeneous catalyst DB1) with a Rh content of 2wt% was finally prepared.

[0248] Following the method of Test Example 1, except that heterogeneous catalyst A was replaced with heterogeneous catalyst DB1, and hydrogenated nitrile rubber was finally obtained.

[0249] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 93.1% and the selectivity was 100%.

[0250] [Test Comparison Example 3]

[0251] The method is the same as in Test Example 5, except that only heterogeneous catalyst D is used, as follows:

[0252] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 9.4g of heterogeneous catalyst D, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0253] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method of Test Example 1. The results showed that the degree of hydrogenation was 58% and the selectivity was 100%.

[0254] [Test Comparison Example 4]

[0255] The method is the same as in Test Example 1, except that only a homogeneous catalyst is used, as follows:

[0256] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.0g of triphenylphosphine, and carry out a catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90℃, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0257] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation (unsaturation) and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 67.2% and the selectivity was 100%.

[0258] [Test Comparison Example 5]

[0259] Take 85g of SiO2 microsphere carrier (particle size 20μm, average pore size 110nm).

[0260] Take 5g of dimethyl dioctadecyl ammonium chloride, add 95g of o-xylene, and mix evenly in 10mL of hydrochloric acid (37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the SiO2 microsphere carrier at 20℃ for 2h, and then dry at 60℃ for 12h.

[0261] Infrared spectrum of surface-treated SiO2 support as shown in the figure Figure 4 As shown.

[0262] As can be seen from Test Examples 1-26 and Comparative Examples 1-4, the present invention employs a method that works synergistically with a homogeneous catalyst to hydrogenate and saturate polymer materials at lower temperatures and pressures. The resulting hydrogenated nitrile rubber product has a high degree of hydrogenation and can also ensure the multiple uses of the heterogeneous catalyst, which is easy to separate and recover.

[0263] pass Figure 1 , Figure 3 To the end Figure 5 It can be seen that surface treatment of the composite oxide support using an impregnation solution containing organic cationic quaternary ammonium salts results in a surface characteristic of the composite oxide support with an infrared spectrum in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1Three characteristic peaks are present at this location. The infrared spectrum of the untreated TiO2-SiO2 composite oxide support differs from that of the surface-treated SiO2 support, which shows peaks in the 620-710 cm⁻¹ range. -1 There are no three characteristic peaks at 2850-2960 cm⁻¹. -1 The three characteristic peaks are also absent. The composite oxide support of this invention can significantly improve the dispersion of active components on the catalyst surface, controlling the active component atomic clusters to be no larger than 5 nm, thereby significantly improving the hydrogenation activity of the catalyst.

[0264] The above description is merely a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, based on the technical teachings provided by the present invention and as common knowledge in the field, other equivalent modifications and improvements can be made, and these should also be considered within the scope of protection of the present invention.

Claims

1. A heterogeneous catalyst, comprising: A composite oxide support of SiO2 and group IVB metal oxides, and an active component Pd and its oxides loaded on the composite oxide support, wherein the group IVB metal oxides are TiO2 and / or ZrO2; the surface properties of the composite oxide support are characterized by an infrared spectrum in the range of 620-710 cm⁻¹. -1 There are three characteristic peaks at 2850-2960 cm⁻¹. -1 There are three characteristic peaks; the composite oxide support is obtained by surface treatment of the composite support of SiO2 and group IVB metal oxides with an impregnation solution containing an organic cationic quaternary ammonium salt; the organic cationic quaternary ammonium salt is a long-chain alkyl quaternary ammonium salt with more than 6 C6.

2. The heterogeneous catalyst according to claim 1, characterized in that, The organic cationic quaternary ammonium salt is selected from dimethyl dioctadecylammonium chloride, hexadecyltrimethylammonium chloride, and C. 12-14 At least one of alkyl dimethyl ethyl benzyl ammonium chloride.

3. The heterogeneous catalyst according to claim 1, characterized in that, Based on the total weight of the composite oxide support, the content of group IVB metal oxides is 5~25wt%, and the content of SiO2 is 75~95wt%; based on the total weight of the heterogeneous catalyst, the content of Pd and its oxides, calculated as Pd, is 0.5~2wt%.

4. The heterogeneous catalyst according to any one of claims 1-3, characterized in that, The heterogeneous catalyst also includes Mo and its oxides supported on the support.

5. The heterogeneous catalyst according to claim 4, characterized in that, The content of Mo and its oxides, calculated as Mo, is 0.1~0.5 wt% based on the total weight of the heterogeneous catalyst.

6. The heterogeneous catalyst according to claim 5, characterized in that, The heterogeneous catalyst has a particle size of 5-30 μm, an average pore size of 100-1200 nm, and a specific surface area of ​​30-200 m². 2 / g; and / or, the atomic cluster particle size of the active component Pd is no greater than 5nm.

7. The heterogeneous catalyst according to claim 6, characterized in that, The atomic cluster size of the active component Pd is 2~5nm.

8. A method for preparing a heterogeneous catalyst according to any one of claims 1-7, comprising the following steps: (1) The SiO2 microsphere carrier is first impregnated with a solution containing group IVB metal compounds, then dried and calcined to obtain a composite carrier, wherein the group IVB metal compounds are titanium-containing compounds and / or zirconium-containing compounds. (2) The composite carrier is surface-treated with an impregnation solution containing organic cationic quaternary ammonium salt to obtain a composite oxide carrier; (3) The composite oxide carrier is second impregnated with a soluble salt of Pd, then dried and calcined.

9. The preparation method according to claim 8, characterized in that, The impregnation solution containing the organic cationic quaternary ammonium salt includes the organic cationic quaternary ammonium salt, a solvent, and an acid.

10. The preparation method according to claim 9, characterized in that, In the impregnation solution containing organic cationic quaternary ammonium salt, the concentration of the quaternary ammonium salt solution is 0.1~10 wt%.

11. The preparation method according to any one of claims 8-10, characterized in that, The surface treatment consists of impregnation and drying.

12. The preparation method according to claim 11, characterized in that, The immersion conditions in the surface treatment include: a temperature of 20~60℃ and a time of 0.5~8h; the drying conditions include: a temperature of 50~120℃ and a time of 2~10h.

13. The preparation method according to any one of claims 8-10, characterized in that, After step (2) and before step (3), the preparation method further includes: dissolving a soluble salt of molybdenum or molybdenum trioxide and impregnating the surface-treated composite oxide carrier to obtain a Mo-modified surface-treated composite oxide carrier.

14. The preparation method according to claim 13, characterized in that, The soluble salt of Mo is selected from at least one of ammonium molybdate and ammonium polymolybdate.

15. The preparation method according to claim 13, characterized in that, The molar ratio of soluble molybdenum salt to SiO2 is 1:1500~2000.

16. The preparation method according to claim 13, characterized in that, The solution used for dissolution is selected from at least one of ammonia, dilute acid solution and alkaline solution.

17. The preparation method according to any one of claims 8-10, characterized in that, The SiO2 microsphere carrier has a particle size of 5-30 μm and / or an average pore size of 100-1200 nm; and / or a specific surface area of ​​30-100 m². 2 / g; And / or, the titanium-containing compound is selected from at least one of titanium sulfate, metatitanic acid, titanium tetrachloride and tetrabutyl titanate; And / or, the zirconium-containing compound is selected from at least one of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride and zirconium oxalate; And / or, the organic cationic quaternary ammonium salt is a long-chain alkyl quaternary ammonium salt with more than 6 carbon atoms; And / or, the soluble salt of said Pd is selected from palladium sulfate, nitrate, halide and palladium acetate.

18. The preparation method according to claim 17, characterized in that, The organic cationic quaternary ammonium salt is selected from dimethyl dioctadecylammonium chloride, hexadecyltrimethylammonium chloride, and C. 12-14 At least one of alkyl dimethyl ethyl benzyl ammonium chloride; And / or, the soluble salt of said Pd is at least one of palladium chloride, palladium nitrate and palladium sulfate.

19. The preparation method according to any one of claims 8-10, characterized in that, The weight ratio of SiO2 microsphere carrier to titanium-containing compound and / or zirconium-containing compound is 7~20:

1.

20. The preparation method according to any one of claims 8-10, characterized in that, The molar ratio of the composite oxide support to the soluble salt of Pd is 1:150~700.

21. The preparation method according to any one of claims 8-10, characterized in that, The conditions for the first impregnation include: a temperature of 20~60℃ and a time of 0.5~8h; and / or, the conditions for the second impregnation include: a temperature of 20~60℃ and a time of 0.5~8h; and / or, the conditions for the first drying include: a temperature of 105~130℃ and a time of 2~8h; and / or, the conditions for the second drying include: a temperature of 105~180℃ and a time of 2~8h; and / or, the conditions for the first calcination include: a temperature of 450~650℃ and a time of 3~8h; and / or, the conditions for the second calcination include: a temperature of 450~650℃ and a time of 3~8h.

22. The heterogeneous catalyst obtained by the preparation method according to any one of claims 8-21.

23. A catalyst composition comprising a homogeneous catalyst and a heterogeneous catalyst as described in any one of claims 1-7 and 22.

24. The catalyst composition according to claim 23, characterized in that, The homogeneous catalyst comprises triphenylphosphine and triphenylphosphine chlorides of platinum group metals.

25. The catalyst composition according to claim 24, characterized in that, The triphenylphosphine chloride of the platinum group metal is triphenylphosphine rhodium chloride and / or triphenylphosphine ruthenium chloride.

26. The catalyst composition according to claim 24, characterized in that, The weight ratio of triphenylphosphine to triphenylphosphine chloride of platinum group metals is 2~5:

1.

27. The catalyst composition according to any one of claims 23-26, characterized in that, The weight ratio of heterogeneous catalyst to homogeneous catalyst is 1:0.01~0.

3.

28. A method for hydrogenating a hydrogenated polymer, comprising: The polymer is dissolved in an organic solvent, and then the catalyst composition of any one of claims 23-27 is added to carry out the reaction.

29. The preparation method according to claim 28, characterized in that, The polymer is nitrile rubber.

30. The preparation method according to claim 28, characterized in that, The organic solvent is selected from at least one of chlorobenzene, acetone, butanone, tetrahydrofuran, dichloromethane, chloroform, cyclohexanone, ethyl acetate, and dimethylformamide.

31. The preparation method according to any one of claims 28-30, characterized in that, The heterogeneous catalyst is used in an amount of 5-20 wt% of the polymer. And / or, the reaction conditions include: a temperature of 30~90℃, a hydrogen pressure of 5~10MPa, and a time of 5~10h.

32. The hydrogenated polymer obtained by the preparation method according to any one of claims 28-31.

33. The hydrogenated polymer according to claim 32, characterized in that, The hydrogenated polymer is hydrogenated nitrile rubber.

34. The heterogeneous catalyst of any one of claims 1-7 and 22, the preparation method of any one of claims 8-21, the catalyst composition of any one of claims 23-27, the hydrogenation method of the hydrogenated polymer of any one of claims 28-31, or the application of the hydrogenated polymer of claim 32 or 33 in rubber products.

35. The application according to claim 34, characterized in that, For application in the field of hydrogenated nitrile butadiene rubber products.

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