Composite oxide support, supported catalyst and hydrogenated nitrile rubber and methods of making and using the same

Abstract

This invention discloses a composite oxide support, a supported catalyst, and hydrogenated nitrile butadiene rubber, as well as their preparation methods and applications. The composite oxide support comprises SiO2 and a group IVB metal oxide, wherein the group IVB metal oxide is TiO2 and / or ZrO2. The surface properties of the composite oxide support are as follows: infrared spectrum 610-720 cm⁻¹ ‑1 There are three characteristic peaks at 2840-2970 cm⁻¹. ‑1 Three characteristic peaks are present. The composite oxide support of the present invention can significantly improve the dispersion of active components on the catalyst surface and significantly improve the hydrogenation activity of the catalyst. By using the supported catalyst of the present invention in synergy with the homogeneous catalyst, polymer materials can be hydrogenated to saturation at lower temperatures and pressures, and the resulting polymer products (especially hydrogenated nitrile rubber) have a high degree of hydrogenation. Moreover, the supported catalyst of the present invention can be reused multiple times, improving the recyclability of the catalyst and reducing the preparation cost.

Description

Technical Field

[0001] This invention relates to a composite oxide support and its preparation method, a supported catalyst and its preparation method, and hydrogenated nitrile butadiene rubber and its preparation method and 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. In homogeneous hydrogenation, the reactants and catalyst are uniformly mixed, reaction conditions are easily controlled, and the product exhibits stable performance. However, a common drawback of homogeneous solution hydrogenation is the difficulty in separating the catalyst from the product. Although various technologies have been developed, such as using ion exchange resins for ion exchange of precious metals, utilizing the complexation of stannous chloride and rhodium catalysts for aqueous phase extraction to recover rhodium, and employing temperature-controlled phase transfer catalysts, these methods are insufficient to completely remove residual precious metal catalysts from the polymer or may generate gels that affect product quality. Furthermore, large-scale industrial production is extremely costly. The residue of precious metals in the hydrogenation product increases production costs and wastes precious metal resources; it also accelerates the aging rate of HNBR, affecting the polymer's machinability.

[0005] Compared to homogeneous hydrogenation catalytic systems, heterogeneous catalytic reaction systems utilize supported noble metal catalysts, effectively solving the problem of catalyst-product separation. This not only enables the reuse of noble metal catalysts but also effectively avoids noble metal residues in the polymer. Currently, the preparation of supported catalysts still 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, noble metals are easily detached and lost from the support surface after vigorous stirring, reducing catalyst availability and affecting the performance of the hydrogenated products. Reon Corporation used SiO2 as a support to support Pd metal for the hydrogenation of nitrile rubber, achieving a hydrogenation degree of over 95% in a single application. However, the catalyst's performance deteriorated with repeated use; for example, activity began to decline after the second use, and the activity decreased significantly after the third and fourth uses, resulting in a marked decrease in the degree of hydrogenation.

[0006] Homogeneous catalytic hydrogenation methods offer high hydrogenation degrees, but catalyst separation is difficult and costs are increasing. Heterogeneous catalyst hydrogenation methods for saturated polymers do not achieve sufficient hydrogenation degrees, and there is a loss of active components during reactor stirring or poor catalyst reuse, resulting in a significant decrease in hydrogenation degree. Therefore, it is necessary to develop a catalyst and related application methods that can ensure high hydrogenation degrees, easy catalyst separation and recovery, and multiple uses of heterogeneous catalysts.

[0007] The catalysts mentioned above all currently use precious metals such as rhodium, palladium, ruthenium, osmium, platinum, and iridium as active components. Existing technologies have not yet disclosed a supported heterogeneous nitrile rubber supported catalyst that uses non-precious metals as active components and has high activity, high selectivity, and high stability. Summary of the Invention

[0008] To address the aforementioned problems in the existing technology, this invention provides a novel composite oxide support with surface characteristics exhibiting an infrared spectrum in the range of 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1Three characteristic peaks are present, which 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 novel multifunctional supported non-precious metal catalyst of this invention uses SiO2 microspheres as a support and non-precious metals as the main active component, resulting in a small particle size. By employing a synergistic method with a homogeneous catalyst, hydrogenation saturation of polymer materials is ensured at relatively low temperatures and pressures, resulting in hydrogenated polymer products (e.g., hydrogenated nitrile rubber) with a high degree of hydrogenation. Moreover, the supported catalyst of this invention can be reused multiple times, and the catalyst composition is easily separated and recovered. More significantly, the use of non-precious metals as the active component in the preparation of the supported catalyst avoids the problem of precious metal active component loss, further improving catalyst recyclability and significantly reducing catalyst cost, thereby reducing the production cost of hydrogenated polymers (e.g., hydrogenated nitrile rubber).

[0009] The first aspect of this invention provides a composite oxide support, characterized in that it comprises: SiO2 and a group IVB metal oxide, wherein the group IVB metal oxide is TiO2 and / or ZrO2, and the surface characteristics of the composite oxide support are such that the infrared spectrum is in the range of 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 Three characteristic peaks are present. In this invention, the infrared spectroscopy measurement conditions are as follows: a Nicolet iS50 infrared spectrometer is used; sample preparation and scanning are performed in attenuated total reflectance mode; the scanning range is 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 610-720 cm⁻¹ -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at this point.

[0010] According to some embodiments of the composite oxide support of the present invention, 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 There are three characteristic peaks at this point.

[0011] According to some embodiments of the composite oxide support of the present invention, the surface characteristics of the composite oxide support are such that the infrared spectrum is within 620±1 cm⁻¹. -1 649±1cm -1 708±1cm -1Characteristic peaks exist at [location]; and / or, the surface properties of the composite oxide support are such that the infrared spectrum is at 2850±1 cm⁻¹. -1 2919±1cm -1 2955±1cm -1 A characteristic peak exists at this location.

[0012] According to some embodiments of the composite oxide support of the present invention, the composite oxide support is obtained by surface treatment of a composite oxide support precursor of SiO2 and group IVB metal oxides using an impregnation solution containing an organic cationic quaternary ammonium salt.

[0013] According to some embodiments of the composite oxide support of the present invention, the organic cationic quaternary ammonium salt is a long-chain alkyl quaternary ammonium salt with more than 6 C6 chains, more preferably a long-chain alkyl halide quaternary ammonium salt with more than 6 C6 chains. More preferably, the halogen is Cl, Br, or I, more preferably Cl. More preferably, the long-chain alkyl group with more than 6 C6 chains is C6-C6. 24 Alkyl groups, more preferably C8-C 22 Alkyl, more preferably C 10 -C 20 Alkyl, more preferably C 12 -C 18 Alkyl group. More preferably, the organic cationic quaternary ammonium salt is selected from dimethyl dioctadecylammonium chloride, hexadecyltrimethylammonium chloride, and C16-alkyl group. 12-14 At least one of alkyl dimethyl ethyl benzyl ammonium chloride.

[0014] In some embodiments of the composite oxide support according to the present invention, the surface treatment is impregnation and drying. That is, the entire process of surface treatment of the composite oxide support precursor using an organic cationic quaternary ammonium salt does not include any high-temperature (e.g., above 300°C) treatment steps such as calcination, roasting, or sintering. In the infrared spectrum of the composite oxide support according to the present invention, in the 610-720 cm⁻¹ range... -1 The three characteristic peaks, for example, at 620-710 cm⁻¹ -1 The three characteristic peaks are located at 620±1 cm. -1 649±1cm -1 708±1cm -1 The characteristic peaks at 2840-2970 cm⁻¹ are mainly attributed to C-halogen (e.g., C-Cl) vibrations; -1 The three characteristic peaks, for example, at 2850-2960 cm⁻¹ -1 The three characteristic peaks are located at 2850±1cm. -1 2919±1cm -1 2955±1cm -1 The characteristic peak at that location is mainly attributed to the CH vibration.

[0015] According to some embodiments of the preparation method of the composite oxide support 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. For example, but not limited to, the content of group IVB metal oxides is 5–20 wt%, 5–15 wt%, 5–10 wt%, 10–25 wt%, 10–20 wt%, 10–15 wt%, 12–25 wt%, 12–20 wt%, 12–15 wt%, 15–25 wt%, 15–20 wt%, 20–25 wt%, etc., and correspondingly, the SiO2 content is 80–95 wt%, 85–95 wt%, 90–95 wt%, 75–90 wt%, 80–90 wt%, 85–90 wt%, 75–88 wt%, 80–88 wt%, 85–88 wt%, 75–85 wt%, 80–85 wt%, 75–80 wt%, etc. Preferably, the content of group IVB metal oxides is 10–25 wt%, and the SiO2 content is 75–90 wt%. Preferably, the content of group IVB metal oxides is greater than 10-25 wt%, and the SiO2 content is 75-less than 90 wt%. Preferably, the content of group IVB metal oxides is 11-25 wt%, and the SiO2 content is 75-89 wt%. Preferably, the content of group IVB metal oxides is 12-25 wt%, and the SiO2 content is 75-88 wt%. Preferably, the content of group IVB metal oxides is 15-25 wt%, and the SiO2 content is 75-85 wt%.

[0016] According to some embodiments of the preparation method of the composite oxide support of the present invention, if the group IVB metal oxide is TiO2 and ZrO2, the ratio of TiO2 to ZrO2 can vary in a wide range, for example, but not limited to, the weight ratio of TiO2 to ZrO2 is 0.01-100:1, 0.05-20:1, 0.1-10:1, 0.3-3:1, 0.5-2:1, 1-100:1, 1-20:1, 1-10:1, 1-3:1, 1-2:1, 0.01-1:1, 0.05-1:1, 0.1-1:1, 0.3-1:1, 0.5-1:1.

[0017] In some embodiments of the preparation method of the composite oxide support according to the present invention, the particle size of the composite oxide 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., including the range between any two of the above values. In the present invention, the particle size of the composite oxide support is measured according to the test method NB / SH / T0951-2017, using a Malvern MS2000 laser particle size analyzer.

[0018] In some embodiments of the preparation method of the composite oxide support according to the present invention, the average pore size of the composite oxide 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, 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., including the range between any two of the above values. In this invention, the average pore size of the composite oxide support 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 automatic mercury porosimetry instrument, the AutoPoreIV 9500 model from Micron Instruments, Inc.

[0019] According to some embodiments of the preparation method of the composite oxide support of the present invention, the specific surface area of ​​the composite oxide support 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, 30~90m 2 / g, 30~80m 2 / g, 30~70m 2 / g, 30~60m 2 / g, 30~50m 2 / g, 30~40m 2 / g, 50~200m 2 / g, 50~150m 2 / g, 50~120m 2 / g, 50~100m 2 / g, 50~90m 2 / g, 50~80m 2 / g, 50~70m 2 / g, 50~60m 2 / g, 80~200m 2 / g, 80~150m 2 / g, 80~120m 2 / g, 80~100m 2 / g, 80~90m 2 / g, 100~200m 2 / g, 100~150m 2 / g, 100~120m 2 / g, 120~200m 2 / g, 120~150m 2 / g, etc., including the range between any two of the above values. In this invention, the specific surface area of ​​the composite oxide carrier is measured according to the mercury porosimetry method of GBT 21650.1-2008, the first part of the determination of pore size distribution and porosity of solid materials by mercury porosimetry and gas adsorption method, using a high-performance fully automatic mercury porosimetry instrument, model AutoPoreIV 9500, manufactured by Micron Instruments, Inc.

[0020] A second aspect of the present invention provides a method for preparing the above-mentioned composite oxide support, comprising the following steps:

[0021] (1) The SiO2 microsphere carrier is first impregnated with a solution containing group IVB metal compounds, then dried and calcined to obtain an oxide composite carrier precursor, wherein the group IVB metal compounds are titanium-containing compounds and / or zirconium-containing compounds.

[0022] (2) The composite oxide carrier precursor is surface-treated with an impregnation solution containing organic cationic quaternary ammonium salt to obtain the composite oxide carrier.

[0023] According to some embodiments of the preparation method of the composite oxide carrier of the present invention, the impregnation solution containing the organic cationic quaternary ammonium salt includes the organic cationic quaternary ammonium salt, a solvent, and an acid.

[0024] In some embodiments of the preparation method of the composite oxide support according to the present invention, the organic cationic quaternary ammonium salt is a long-chain alkyl quaternary ammonium salt with more than 6 C6 chains, more preferably a long-chain alkyl halide quaternary ammonium salt with more than 6 C6 chains. More preferably, the halogen is Cl, Br, or I, more preferably Cl. More preferably, the long-chain alkyl group with more than 6 C6 chains is C6-C 24 Alkyl groups, more preferably C8-C 22 Alkyl, more preferably C 10 -C 20 Alkyl, more preferably C 12 -C 18 Alkyl group. More preferably, the organic cationic quaternary ammonium salt is selected from dimethyl dioctadecylammonium chloride, hexadecyltrimethylammonium chloride, and C16-alkyl group. 12-14 At least one of alkyl dimethyl ethyl benzyl ammonium chloride.

[0025] In some embodiments of the preparation method of the composite oxide support according to the present invention, the solvent is selected from at least one of deionized water, methanol, ethanol, acetone, butanone, tetrahydrofuran, o-xylene, p-xylene, and pyridine. Preferably, the solvent is selected from at least one of o-xylene, p-xylene, and pyridine. More preferably, the solvent is o-xylene or pyridine.

[0026] In some embodiments of the preparation method of the composite oxide support according to the present invention, the acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, and citric acid. Preferably, the acid is hydrochloric acid. More preferably, the concentration of the acid is 1 to 98.3 wt%.

[0027] In some embodiments of the preparation method of the composite oxide support 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.

[0028] In some embodiments of the preparation method of the composite oxide support 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 0.5–8 h; the drying conditions include a temperature of 50–120°C and a time of 2–10 h. Throughout the entire process of surface treatment of the composite oxide support precursor using an organic cationic quaternary ammonium salt, no high-temperature (e.g., above 300°C) treatment steps are included, such as calcination, roasting, or sintering. Thus, the groups of the organic cationic quaternary ammonium salt and acids (such as amino, hydrogen, halide, alkyl, etc.) can be retained on the composite oxide support, and these groups can interact with the active components, thereby promoting the dispersion of the active components.

[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] In some embodiments of the preparation method of the composite oxide support 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., including the range between any two of the above values. In the present 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.

[0031] In some embodiments of the preparation method of the composite oxide support 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, 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., including the range between any two of the above values. 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.

[0032] According to some embodiments of the preparation method of the composite oxide support of the present invention, the specific surface area of ​​the SiO2 microsphere support 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, 30~90m 2 / g, 30~80m 2 / g, 30~70m 2 / g, 30~60m 2 / g, 30~50m 2 / g, 30~40m 2 / g, 50~200m 2 / g, 50~150m 2 / g, 50~120m 2 / g, 50~100m2 / g, 50~90m 2 / g, 50~80m 2 / g, 50~70m 2 / g, 50~60m 2 / g, 80~200m 2 / g, 80~150m 2 / g, 80~120m 2 / g, 80~100m 2 / g, 80~90m 2 / g, 100~200m 2 / g, 100~150m 2 / g, 100~120m 2 / g, 120~200m 2 / g, 120~150m 2 / g, etc., including the range between any two of the above values. 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, part one, GBT 21650.1-2008, using a high-performance fully automated mercury porosimetry instrument, model AutoPoreIV 9500, manufactured by Micron Instruments, Inc.

[0033] According to some embodiments of the preparation method of the composite oxide support 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 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 The resolution is 4cm. -1 The number of scans was 32.

[0034] In this invention, the silica microsphere carrier can be obtained commercially (e.g., from Shandong Bangkai Materials Co., Ltd., Beijing Bailingwei Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., etc.) or in-house.

[0035] In some embodiments of the preparation method of the composite oxide support 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, titanium sulfate or titanium tetrachloride can be dissolved in water. Another example is that metatitanic acid can be dissolved in a dilute sulfuric acid solution. Yet another example is that tetrabutyl titanate can be dissolved in an ethanol solution.

[0036] In some embodiments of the method for preparing the composite oxide support 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. For example, the above-mentioned zirconium compound can be dissolved in water.

[0037] In some embodiments of the preparation method of the composite oxide support according to the present invention, the concentration of the titanium compound and / or zirconium compound in the solution is 0.1 to 1.0 mol / L. For example, but not limited to, 0.1 to 0.8 mol / L, 0.1 to 0.6 mol / L, 0.1 to 0.4 mol / L, 0.2 to 1.0 mol / L, 0.2 to 0.8 mol / L, 0.2 to 0.6 mol / L, 0.2 to 0.4 mol / L, 0.3 to 1.0 mol / L, 0.3 to 0.8 mol / L, 0.3 to 0.6 mol / L, 0.3 to 0.4 mol / L, 0.4 to 1.0 mol / L, 0.4 to 0.8 mol / L, 0.4 to 0.6 mol / L, 0.5 to 1.0 mol / L, 0.5 to 0.8 mol / L, 0.5 to 0.6 mol / L, etc., including any two of the above values.

[0038] In some embodiments of the preparation method of the composite oxide carrier according to the present invention, the molar ratio of SiO2 microsphere carrier to group IVB metal compound is 3-40:1, for example 4-26:1, 5-30:1, 6-39:1, wherein the molar amount of SiO2 microsphere carrier is calculated as Si, and the amount of titanium compound and / or zirconium compound is calculated as titanium and / or zirconium element.

[0039] According to some embodiments of the preparation method of the composite oxide carrier 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.

[0040] According to some embodiments of the preparation method of the composite oxide support of the present invention, the first drying conditions include: a temperature of 105-130°C and a time of 2-8 hours.

[0041] According to some embodiments of the preparation method of the composite oxide support of the present invention, the conditions for the first calcination include: a temperature of 450-650°C and a time of 3-8 hours.

[0042] A third aspect of the present invention provides a supported catalyst, comprising: the aforementioned composite oxide support, and an active component Cu and its oxide supported on the support; the atomic cluster particle size of the active component copper is not greater than 5 nm; the content of Cu and its oxide, based on CuO and the total weight of the supported catalyst, is 5-25 wt%, preferably 8-25 wt%, preferably 10-25 wt%, and preferably 12-25 wt%.

[0043] According to some embodiments of the supported catalyst of the present invention, the particle size of the supported catalyst 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., including the range between any two of the above values. In the present invention, the particle size of the catalyst is measured according to the test method NB / SH / T0951-2017, using a Malvern MS2000 laser particle size analyzer.

[0044] According to some embodiments of the supported catalyst of the present invention, the average pore size of the supported 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, 400–1200 nm, 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., including the range between any two of the above values. 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.

[0045] According to some embodiments of the supported catalyst of the present invention, the specific surface area of ​​the supported 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, 30~90m 2 / g, 30~80m 2 / g, 30~70m 2 / g, 30~60m 2 / g, 30~50m 2 / g, 30~40m 2 / g, 50~200m 2 / g, 50~150m 2 / g, 50~120m 2 / g, 50~100m 2 / g, 50~90m2 / g, 50~80m 2 / g, 50~70m 2 / g, 50~60m 2 / g, 80~200m 2 / g, 80~150m 2 / g, 80~120m 2 / g, 80~100m 2 / g, 80~90m 2 / g, 100~200m 2 / g, 100~150m 2 / g, 100~120m 2 / g, 120~200m 2 / g, 120~150m 2 / g, etc., including the range between any two of the above values. 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 mercury porosimetry and gas adsorption method, part one, using a high-performance fully automatic mercury porosimetry instrument, model AutoPoreIV 9500, manufactured by Micron Instruments, USA.

[0046] In some embodiments of the supported catalyst according to the present invention, the atomic cluster particle size of the active component copper is 2–5 nm. This is determined by transmission electron microscopy (TEM) characterization, measured according to a scale bar.

[0047] According to some embodiments of the supported catalyst of the present invention, the supported catalyst is substantially free of precious metals such as rhodium, palladium, ruthenium, osmium, platinum, iridium, etc. The term "substantially free" means that the content of precious metals such as rhodium, palladium, ruthenium, osmium, platinum, iridium, etc., in the supported catalyst is less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0.2 wt%, preferably less than 0.1 wt%, and preferably 0%. Preferably, the supported catalyst is completely free of precious metals such as rhodium, palladium, ruthenium, osmium, platinum, iridium, etc.

[0048] According to some embodiments of the supported catalyst of the present invention, the supported catalyst is substantially free of non-precious metals other than copper, titanium, and zirconium, such as cobalt, nickel, molybdenum, zinc, and iron. The term "substantially free" means that the content of non-precious metals other than copper, titanium, and zirconium, such as cobalt, nickel, molybdenum, zinc, and iron, in the supported catalyst is less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0.2 wt%, preferably less than 0.1 wt%, and preferably 0%. Preferably, the supported catalyst is completely free of non-precious metals other than copper, titanium, and zirconium, such as cobalt, nickel, molybdenum, zinc, and iron.

[0049] According to some embodiments of the supported catalyst of the present invention, the supported catalyst is substantially free of metals other than copper, titanium, and zirconium. The term "substantially free" means that the content of metals other than copper, titanium, and zirconium in the supported catalyst is less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0.2 wt%, preferably less than 0.1 wt%, and most preferably 0%. Preferably, the supported catalyst is completely free of metals other than copper, titanium, and zirconium.

[0050] The fourth aspect of the present invention provides a method for preparing the above-mentioned supported catalyst, comprising the following steps: second impregnating the above-mentioned composite oxide support with a solution of Cu soluble salt, followed by second drying and second calcination.

[0051] In some embodiments of the preparation method of the supported catalyst according to the present invention, the molar ratio of the composite oxide support to the soluble salt of Cu is 1:0.03 to 0.6, for example 1:0.03 to 0.4, 1:0.04 to 0.25, 1:0.05 to 0.32, or 1:0.06 to 0.5. The molar amount of the composite oxide support is expressed as Si, and the soluble salt of Cu is expressed as Cu elemental.

[0052] In some embodiments of the method for preparing the supported catalyst according to the present invention, the soluble salt of Cu is selected from at least one of copper chloride, copper sulfate, copper nitrate, copper acetate, and disodium ethylenediaminetetraacetate (EDTA-Cu-15).

[0053] According to some embodiments of the preparation method of the supported 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.

[0054] According to some embodiments of the preparation method of the supported catalyst of the present invention, the conditions for the second drying include: a temperature of 105-180°C and a time of 2-8 hours.

[0055] According to some embodiments of the preparation method of the supported 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.

[0056] In some embodiments of the preparation method of the supported catalyst according to the present invention, the amounts of SiO2 microsphere support and titanium 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%.

[0057] In some embodiments of the preparation method of the supported catalyst according to the present invention, the amount of the soluble salt of the second impregnation of Cu in the composite oxide support of SiO2, TiO2 and / or ZrO2 satisfies the requirement that the CuO content, calculated as CuO, is 5-25 wt% based on the total weight of the supported catalyst. Examples include, but are not limited to, 5-20 wt%, 5-15 wt%, 5-10 wt%, 10-25 wt%, 10-20 wt%, 10-15 wt%, 12-25 wt%, 12-20 wt%, 12-15 wt%, 15-25 wt%, 15-20 wt%, 20-25 wt%, etc.

[0058] A fifth aspect of the present invention provides a catalyst composition comprising a homogeneous catalyst and the above-described supported catalyst.

[0059] 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.

[0060] Specifically, transition metal ruthenium carbene complex catalysts include, but are not limited to, the structures of formulas (1) to (7):

[0061]

[0062] The structure of Grubbs catalysts includes, but is not limited to, that shown in formula (8):

[0063]

[0064] 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.

[0065] 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.

[0066] 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.

[0067] A sixth aspect of the present invention provides a method for hydrogenating a polymer, comprising: dissolving the polymer in an organic solvent, then adding the aforementioned catalyst composition, and reacting the polymer with hydrogen in the presence of the catalyst composition. The hydrogenation method is typically carried out in a reaction vessel. First, the polymer dissolved in the organic solvent is added to the reaction vessel, followed by the addition of the catalyst composition. Then, the reaction vessel is closed, and hydrogen is introduced to replace the air, allowing the polymer to react with hydrogen in the presence of the catalyst composition.

[0068] In some embodiments of the hydrogenation method for polymers according to the present invention, the amount of the supported catalyst is 5-20 wt% of the polymer. For example, 5-20 wt%, 5-15 wt%, 5-10 wt%, 10-20 wt%, 10-15 wt%, 15-20 wt%, etc.

[0069] According to some embodiments of the hydrogenation method for polymers 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.

[0070] According to some embodiments of the hydrogenation method for polymers described in this invention, the amount of polymer dissolved in organic solvent is such that the content of the polymer in the organic solvent is 0.1 to 10 wt%. For example, 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%, 9–10 wt%, etc., based on the total weight of the polymer and solvent.

[0071] According to some embodiments of the hydrogenation method for the polymer of the present invention, the polymer is an unsaturated copolymer of a conjugated diene and a copolymerizable monomer. The conjugated diene is selected from at least one of butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene, preferably butadiene and / or isoprene, and more preferably butadiene. The copolymerizable monomer is selected from at least one of acrylonitrile, methacrylonitrile, styrene, propyl acrylate, butyl acrylate, propyl methacrylate, and butyl methacrylate, preferably acrylonitrile and / or methacrylonitrile, and more preferably acrylonitrile.

[0072] According to some embodiments of the hydrogenation method for the polymer described in this invention, the polymer is nitrile rubber. In this art, nitrile rubber refers to a copolymer polymerized from acrylonitrile and butadiene monomers.

[0073] According to some embodiments of the hydrogenation method for polymers described in this invention, there are no particular limitations on nitrile rubber; that is, the hydrogenation method of this invention can be used for the hydrogenation of almost all nitrile rubbers. For example, nitrile rubber can be obtained commercially (e.g., from Reynolds Corporation (such as grades DN series, 1000x132, 1001CG, 10001LG, 1031, 1041, 1041L, 1042, 1002, 1032J, 1022x59, 1052J, 1032-45, 1092-80, 1043, N917, 1094-80, 1014, 1034-60) or by Qilu Petrochemical) or by self-production.

[0074] For example, the acrylonitrile content of nitrile rubber can be 15-55 wt%, such as 19-51 wt%, 20-55 wt%, 25-55 wt%, 30-55 wt%, 35-55 wt%, 40-55 wt%, 45-55 wt%, 20-50 wt%, 25-50 wt%, 30-50 wt%, 35-50 wt%, 40-50 wt%, 45-50 wt%, 20- 45wt%, 25-45wt%, 30-45wt%, 35-45wt%, 40-45wt%, 20-40wt%, 25-40wt%, 30-40wt%, 35-40wt%, 20-35wt%, 25-35wt%, 30-35wt%, 20-25wt%, 20-30wt%, 25-30wt%, etc., including the range between any two of the above values.

[0075] For example, the Mooney viscosity (ML, 100℃, 1+4) of nitrile rubber can be 20-100, such as 20-40, 20-60, 20-80, 25-35, 25-55, 25-75, 25-95, 30-50, 30-70, 30-90, 35-45, 35-65, 35-85, 40-60, 40-80, 40-100, 45-55, 45-75, 45-95, 50-70, 50-90, 55-65, 55-85, 60-80, 60-100, 65-75, 65-95, 70-90, 75-85, 80-100, 85-95, 90-100, etc., including the range between any two of the above values.

[0076] In some embodiments of the hydrogenation method for polymers 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.

[0077] According to some embodiments of the hydrogenation method for polymers described in this invention, the hydrogenation method for polymers may further include: after the reaction is completed, recovering the supported catalyst by filtration or centrifugation, and recovering the homogeneous catalyst by ion exchange with an ion exchange resin.

[0078] According to some embodiments of the hydrogenation method for polymers described in this invention, the degree of hydrogenation is at least 90%, for example, but not limited to, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, and at least 99%. The test method for the degree of hydrogenation is SH / T 1762-2008 / ISO 14558:2000.

[0079] In some embodiments of the hydrogenation method for polymers according to the present invention, the selectivity is at least 98%, for example, but not limited to, at least 99%, at least 99.1%, at least 99.2%, at least 99.3%, at least 99.4%, at least 99.5%, at least 99.6%, at least 99.7%, at least 99.8%, at least 99.9%, and 100%. The selectivity is tested using infrared spectroscopy, and the instrument used is a Nicolet 560 Fourier transform infrared spectrometer manufactured by Nicolet Corporation, USA.

[0080] The seventh aspect of the present invention provides a hydrogenated polymer obtained by the above-described hydrogenation method, preferably a hydrogenated nitrile rubber.

[0081] According to some embodiments of the hydrogenated polymer, preferably hydrogenated nitrile butadiene rubber, the degree of hydrogenation of the hydrogenated polymer, preferably hydrogenated nitrile butadiene rubber, is at least 90%, for example, but not limited to at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, and at least 99%. The test method for the degree of hydrogenation is SH / T 1762-2008 / ISO 14558:2000.

[0082] According to some embodiments of the hydrogenated nitrile butadiene rubber of the present invention, the hydrogenated nitrile butadiene rubber has excellent properties such as good oil resistance, heat resistance, chemical corrosion resistance, odor resistance, high tear resistance and abrasion resistance.

[0083] The eighth aspect of the present invention provides the above-described composite oxide support, the composite oxide support obtained by the above-described method for preparing the composite oxide support, the above-described supported catalyst, the supported catalyst obtained by the above-described method for preparing the supported catalyst, the above-described catalyst composition, the hydrogenated polymer obtained by the above-described method for hydrogenating the polymer, or the above-described hydrogenated polymer in the manufacture of rubber products or thereof, particularly in the field of hydrogenated nitrile rubber products or thereof.

[0084] The beneficial effects of this invention are:

[0085] (1) Modifying the composite 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 Cu atom clusters of active components to be no larger than 5 nm, thereby significantly improving the hydrogenation activity of the catalyst.

[0086] (2) The supported catalyst prepared based on the composite support of SiO2 treated with organic cation quaternary ammonium salt and group IVB metal oxide has a pore structure suitable for hydrogenation of macromolecules such as nitrile rubber. TiO2 and / or ZrO2 on the surface of the support can improve the hydrogenation activity of the catalyst. The catalyst has good hydrogenation activity and stability.

[0087] (3) By combining the supported catalyst of the present invention with the homogeneous catalyst, the polymer material can be hydrogenated to saturation at a lower temperature and pressure, and the hydrogenated polymer (e.g., hydrogenated nitrile rubber) product obtained has a higher degree of hydrogenation.

[0088] (4) After the reaction is completed, the supported catalyst is recovered by filtration or centrifugation, and the homogeneous catalyst is recovered by ion exchange resin. This ensures that the supported catalyst can be reused multiple times and the catalyst is easy to separate and recover.

[0089] (5) The hydrogenation method of hydrogenated polymer (e.g., hydrogenated nitrile rubber) using the supported catalyst of the present invention is the first to use non-precious metals as active components to prepare a supported catalyst for hydrogenation of nitrile rubber, which avoids the problem of loss of precious metal active components, further improves the recyclability of the catalyst, significantly reduces the cost of the catalyst, and thus reduces the production cost of hydrogenated polymer (hydrogenated nitrile rubber). Attached Figure Description

[0090] Figure 1 The image shows the infrared spectrum of the composite oxide support in Example 1 of this invention.

[0091] Figure 2 This is a TEM image of the supported catalyst A in Example 13 of the present invention.

[0092] Figure 3 The infrared spectrum of the untreated TiO2-SiO2 composite support in Comparative Example 1 was obtained for testing.

[0093] Figure 4 The infrared spectrum of the surface-treated SiO2 support in Comparative Example 5 was obtained for testing.

[0094] Figure 5 The infrared spectra of the carriers of Example 1, Comparative Example 1, and Comparative Example 5 are shown in comparison. Detailed Implementation

[0095] 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.

[0096] In the following embodiments and comparative examples,

[0097] (1) The SiO2 microsphere carrier was purchased from Shandong Bangkai Materials Co., Ltd.

[0098] (2) Dimethyl dioctadecyl ammonium chloride, purchased from Beijing Bailingwei Technology Co., Ltd., CAS No. 61789-80-8.

[0099] (3) Hexadecyltrimethylammonium chloride, purchased from Beijing Bailingwei Technology Co., Ltd., CAS No. 112-02-7.

[0100] (4)C 12-14 -Alkyl dimethyl ethyl benzyl ammonium chloride, purchased from Beijing Bailingwei Technology Co., Ltd., CAS No. 85409-23-0.

[0101] (5) The content of Cu and its oxides, calculated as CuO, was obtained by ICP atomic emission spectrometry using an Optima 8300 instrument from Platinum Elmer (PE) in accordance with standard JY / T 0567-2020.

[0102] (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 Unico UV-2100 spectrophotometer.

[0103] (7) Similarly, the ZrO2 content was determined using a spectrophotometer.

[0104] (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.

[0105] (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.

[0106] (10) The atomic cluster size of the active component copper was characterized by transmission electron microscopy (TEM) and measured according to the scale bar.

[0107]

Example 1

[0108] SiO2 microspheres (particle size 20 μm, average pore size 110 nm, specific surface area 78 m²) were used as carriers. 2 85g of TiO2 was impregnated with 420mL of a 0.45mol / L titanium sulfate aqueous solution at 25℃ for 6h. The precipitate was then dried at 110℃ for 6h and calcined at 550℃ for 5h. A TiO2-SiO2 composite support with a TiO2 content of 15wt% (SiO2 content of 85wt%) was obtained.

[0109] Take 5g of dimethyl dioctadecyl ammonium chloride, add 95g of o-xylene, and mix evenly with 10mL of hydrochloric acid (mass fraction 37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at 20℃. After impregnation for 2h, dry at 60℃ for 12h to obtain the TiO2-SiO2 composite oxide support.

[0110] 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at 620 cm⁻¹. Specifically, the infrared spectrum shows three peaks at 620 cm⁻¹. -1 649cm -1 708cm -1Characteristic peaks exist at 2850 cm⁻¹; and at 2850 cm⁻¹ -1 2919cm -1 2955cm -1 A characteristic peak exists at this location.

[0111]

Example 2

[0112] 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 aqueous solution of titanium sulfate is replaced with 420 mL of a 0.86 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%).

[0113] Take 4g of dimethyl dioctadecyl ammonium chloride, add 96g of o-xylene, and mix evenly with 8mL of hydrochloric acid (mass fraction 37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at 20℃. After impregnation for 2h, dry at 60℃ for 12h to obtain the TiO2-SiO2 composite oxide support.

[0114] 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at this point.

[0115]

Example 3

[0116] 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 aqueous solution of titanium sulfate is replaced with 398 mL of a 0.38 mol / L aqueous solution of titanium tetrachloride to obtain a TiO2-SiO2 composite support with a TiO2 content of 12 wt% (SiO2 content of 88 wt%).

[0117] Take 3g of dimethylbis(octadecyl)ammonium chloride, add 97g of o-xylene, and mix evenly with 7mL of hydrochloric acid (37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at 20℃. After impregnation for 2h, dry at 60℃ for 12h to obtain the TiO2-SiO2 composite oxide support.

[0118] 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 610-720 cm⁻¹. -1There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at this point.

[0119]

Example 4

[0120] 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 aqueous solution of titanium sulfate is replaced with 360 mL of an ethanol solution of 0.63 mol / L tetrabutyl titanate, to obtain a TiO2-SiO2 composite support with a TiO2 content of 18 wt% (SiO2 content of 82 wt%).

[0121] Take 2g of dimethylbis(octadecyl)ammonium chloride, add 98g of o-xylene, and mix evenly with 5mL of hydrochloric acid (37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at 20℃. After impregnation for 2h, dry at 60℃ for 12h to obtain the TiO2-SiO2 composite oxide support.

[0122] 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at this point.

[0123]

Example 5

[0124] 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 aqueous solution of titanium sulfate is replaced with 123 mL of an ethanol solution of 0.51 mol / L tetrabutyl titanate to obtain a TiO2-SiO2 composite support with a TiO2 content of 5 wt% (SiO2 content of 95 wt%).

[0125] Take 1g of hexadecyltrimethylammonium chloride, add 99g of o-xylene, and mix evenly with 3mL of hydrochloric acid (mass fraction 37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at 20℃. After impregnation for 4h, dry at 80℃ for 12h to obtain the TiO2-SiO2 composite oxide support.

[0126] 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1There are three characteristic peaks at this point.

[0127]

Example 6

[0128] The preparation method of the TiO2-SiO2 composite support is the same as in Example 1, except that the calcination at 550℃ for 5 hours is replaced by calcination at 650℃ for 7 hours. A TiO2-SiO2 composite support with a TiO2 content of 15 wt% (SiO2 content of 85 wt%) is obtained.

[0129] Take 5g of C 12-14 1-alkyl dimethyl ethyl benzyl ammonium chloride, 95g o-xylene, and 10mL hydrochloric acid (37wt%) were mixed evenly to prepare an impregnation solution. The TiO2-SiO2 composite support was impregnated at 40℃ for 2h and then dried at 100℃ for 12h to obtain the TiO2-SiO2 composite oxide support.

[0130] 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at this point.

[0131]

Example 7

[0132] Following the method of Example 1, except that the aqueous solution of titanium sulfate was replaced with 420 mL of an aqueous solution of zirconium tetrachloride with a concentration of 0.29 mol / L, 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.

[0133] Take 5g of dimethyl dioctadecyl ammonium chloride, add 95g of o-xylene, and mix evenly with 10mL of hydrochloric acid (mass fraction 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.

[0134] 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at this point.

[0135]

Example 8

[0136] Take 85g of SiO2 microsphere carrier and impregnate it with 280mL of a 0.45mol / L titanium sulfate aqueous solution for 6 hours at 25℃. Dry the precipitate at 110℃ for 6 hours and calcine it at 550℃ for 5 hours. Then impregnate it with 300mL of a 0.14mol / L zirconium nitrate aqueous solution for 4 hours at 25℃. Dry the precipitate at 110℃ for 8 hours and calcine it at 550℃ for 6 hours.

[0137] 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.

[0138] Take 5g of dimethylbis(octadecyl)ammonium chloride, add 95g of o-xylene, and mix evenly with 10mL of hydrochloric acid (37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-ZrO2-SiO2 composite support at 20℃. After impregnation for 2h, dry at 60℃ for 12h to obtain the TiO2-ZrO2-SiO2 composite oxide support.

[0139] 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at this point.

[0140]

Example 9

[0141] 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 particle size of 10 μm, an average pore size of 200 nm, and a specific surface area of ​​60 m². 2 / g of SiO2 microsphere carrier.

[0142] 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at this point.

[0143]

Example 10

[0144] 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 particle size of 5 μm, an average pore size of 120 nm, and a specific surface area of ​​75 m². 2 / g of SiO2 microsphere carrier.

[0145] 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at this point.

[0146]

Example 11

[0147] 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 particle size of 30 μm, an average pore size of 1000 nm, and a specific surface area of ​​37 m². 2 / g of SiO2 microsphere carrier.

[0148] 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at this point.

[0149]

Example 12

[0150] The preparation method of the TiO2-SiO2 composite oxide support is the same as in Example 1, except that the solvent in the impregnation solution is replaced by pyridine instead of o-xylene.

[0151] 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at this point.

[0152]

Example 13

[0153] 100g of the composite oxide support prepared in Examples 1-12 was added to 500mL of an aqueous solution of copper nitrate with a Cu content (calculated as CuO) of 5.26-33.33g. The solutions were impregnated at 25°C for 180 minutes, dried at 110°C for 6 hours, and then calcined at 500°C for 4 hours to prepare Cu / TiO2-SiO2 catalysts (supported catalysts Al, L, M, N, O) with a Cu and its oxide content of 5-25wt% (calculated as CuO). See Table 1 for details.

[0154] The prepared supported catalyst A was characterized by TEM, and the results are shown in the figure. Figure 2 ,Depend on Figure 2It can be seen that the active components are uniformly dispersed, and the atomic cluster particle size of the active components is 2-5 nm, with an average particle size of 3.3 nm.

[0155]

Example 13

[0156] 100g of the composite oxide support prepared in Example 1 was added to 500mL of an aqueous solution of copper nitrate containing 32g of Cu, impregnated at 20°C for 180 minutes, dried at 110°C for 6 hours, and then calcined at 600°C for 6 hours to prepare a Cu / TiO2-SiO2 catalyst (supported catalyst J) with a Cu and its oxide content of 24wt% (calculated as CuO). See Table 1 for details.

[0157]

Example 14

[0158] 100g of the composite oxide support prepared in Example 1 was added to 500mL of an aqueous solution of copper nitrate containing 32g of Cu, impregnated at 30°C for 180 minutes, dried at 110°C for 6 hours, and then calcined at 650°C for 7 hours to prepare a Cu / TiO2-SiO2 catalyst (supported catalyst K) with a Cu and its oxide content of 24wt% (calculated as CuO). See Table 1 for details.

[0159] Table 1

[0160]

[0161]

[0162] The particle size, average pore size, and specific surface area of ​​the supported catalyst AN were tested, and the results are shown in Table 2.

[0163] The average particle size was determined using a Malvern MS2000 laser particle size analyzer according to the test method in NB / SH / T 0951-2017.

[0164] The average pore size and specific surface area were determined according to the mercury porosimetry method and gas adsorption method for determining the pore size distribution and porosity of solid materials, as per GB / T 21650.1-2008. The mercury porosimetry method was used in the first part of the standard, which was a high-performance fully automatic mercury porosimetry instrument, the AutoPoreIV 9500 model from Micron Instruments, Inc.

[0165] Table 2

[0166] Supported catalyst number Particle size, μm Average pore size, nm <![CDATA[Specific surface area, m 2 / g]]> A 20 102 47 B 10 100 51 C 5 104 55 D 20 103 54 E 20 102 65 F 22 106 52 G 20 102 55 H 20 103 54 I 20 100 51 J 20 104 51 K 20 104 52 L 10 186 41 M 5 107 46 N 30 983 36

[0167]

Test Example 1

[0168] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of supported 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.

[0169] The hydrogenated nitrile rubber obtained was tested for its degree of hydrogenation. The test method was SH / T 1762-2008 / ISO 14558:2000 (measurement of unsaturation). The results showed that the degree of hydrogenation was 95.2%.

[0170] 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%.

[0171]

Test Example 2

[0172] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of supported 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.

[0173] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 96.1% and the selectivity was 100%.

[0174]

Test Example 3

[0175] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of supported 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.

[0176] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 93.8% and the selectivity was 100%.

[0177]

Test Example 4

[0178] Take 2L of 3wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of supported 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.

[0179] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 97.1% and the selectivity was 100%.

[0180]

Test Example 5

[0181] Take 2L of 3wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of supported 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.

[0182] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 97.6% and the selectivity was 100%.

[0183]

Test Example 6

[0184] After the reaction in Test Example 5 was completed, the supported catalyst A 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 hydrogenation catalytic performance. The experiment was repeated 4 times. The results of the degree of hydrogenation (tested 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.

[0185] Table 3

[0186] Reuse once Reuse twice Reuse 3 times Reused 4 times Hydrogenation degree 94.5％ 93.6％ 93.3％ 92.8％ Selective 100％ 100％ 100％ 100％

[0187]

Test Example 7

[0188] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of supported 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.

[0189] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 97.6% and the selectivity was 100%.

[0190]

Test Example 8

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

[0192] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 91.2% and the selectivity was 100%.

[0193]

Test Example 9

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

[0195] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation according to the method in Test Example 1. The results showed that the degree of hydrogenation was 94.1% and the selectivity was 100%.

[0196]

Test Example 10

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

[0198] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 95.1% and the selectivity was 100%.

[0199]

Test Example 11

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

[0201] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 95.8% and the selectivity was 100%.

[0202]

Test Example 12

[0203] Following the method of Test Example 1, except that supported catalyst A was replaced with supported catalyst I, and hydrogenated nitrile rubber was finally obtained.

[0204] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 95.4% and the selectivity was 100%.

[0205]

Test Example 13

[0206] Following the method of Test Example 1, except that the supported catalyst A was replaced with the supported catalyst J, and hydrogenated nitrile rubber was finally obtained.

[0207] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 95.7% and the selectivity was 100%.

[0208]

Test Example 14

[0209] Following the method of Test Example 1, except that the supported catalyst A was replaced with the supported catalyst K, and hydrogenated nitrile rubber was finally obtained.

[0210] The obtained hydrogenated nitrile rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 94.8% and the selectivity was 100%.

[0211]

Test Example 15

[0212] Following the method of Test Example 1, except that the supported catalyst A was replaced with the supported catalyst L, and hydrogenated nitrile rubber was finally obtained.

[0213] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 95.3% and the selectivity was 100%.

[0214]

Test Example 16

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

[0216] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 95.0% and the selectivity was 100%.

[0217]

Test Example 17

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

[0219] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 96.1% and the selectivity was 100%.

[0220]

Test Example 18

[0221] 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.

[0222] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 93.9% and the selectivity was 100%.

[0223]

Test Example 19

[0224] 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.

[0225] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 91.7% and the selectivity was 100%.

[0226]

Test Example 20

[0227] 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.

[0228] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 90.2% and the selectivity was 100%.

[0229]

Test Example 21

[0230] 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.

[0231] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 88.2% and the selectivity was 100%.

[0232]

Test Example 22

[0233] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of supported catalyst A, 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.

[0234] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 95.3% and the selectivity was 100%.

[0235]

Test Example 23

[0236] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of supported catalyst A, 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.

[0237] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 95.4% and the selectivity was 100%.

[0238]

Test Example 24

[0239] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of supported catalyst A, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 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.

[0240] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 95.3% and the selectivity was 100%.

[0241]

Test Example 25

[0242] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 12g of supported catalyst A, 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.

[0243] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 98.9% and the selectivity was 100%.

[0244]

Test Example 26

[0245] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of supported catalyst A, 0.08g of homogeneous catalyst triphenylphosphine rhodium chloride, and 0.32g 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.

[0246] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 91.3% and the selectivity was 100%.

[0247]

Test Example 27

[0248] Take 2L of 4wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 8g of supported catalyst A, 0.7g of homogeneous catalyst triphenylphosphine ruthenium chloride, and 1.5g 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.

[0249] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 95.2% and the selectivity was 100%.

[0250]

Test Example 28

[0251] Following the method of Test Example 1, except that the supported catalyst A was replaced with the supported catalyst O, and hydrogenated nitrile rubber was finally obtained.

[0252] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 95.7% and the selectivity was 100%.

[0253] [Test Comparison Example 1]

[0254] 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.

[0255] The active component was then loaded according to the method in Example 12, and a Cu / TiO2-SiO2 catalyst with a Cu content of 24 wt% was finally prepared. The particle size of the Cu atom clusters was 20–50 nm.

[0256] Following the method in Test Example 1, hydrogenated nitrile butadiene rubber was finally obtained.

[0257] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 88.2% and the selectivity was 99%.

[0258] [Test Comparison Example 2]

[0259] Using the TiO2-SiO2 composite oxide support from Example 1, and following the method of Example 5, except that the copper nitrate solution was replaced with a nickel nitrate solution, a Ni / ZrO2-SiO2 catalyst (supported catalyst DB1) with a Ni content of 24 wt% was finally prepared. The particle size of the Ni atom clusters was 10–30 nm.

[0260] Following the method of Test Example 1, except that the supported catalyst A was replaced with the supported catalyst DB1, and hydrogenated nitrile rubber was finally obtained.

[0261] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 78% and the selectivity was 82.5%.

[0262] [Test Comparison Example 3]

[0263] The method is the same as in Test Example 1, except that only supported catalyst A is used, as follows:

[0264] Take 2L of 3wt% NBR chlorobenzene solution (using chlorobenzene to dissolve nitrile rubber), add 9.4g of supported catalyst A, 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.

[0265] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation and selectivity according to the method in Test Example 1. The results showed that the degree of hydrogenation was 57.6% and the selectivity was 100%.

[0266] [Test Comparison Example 4]

[0267] The method is the same as in Test Example 5, except that only a homogeneous catalyst is used, as follows:

[0268] Take 2L of 3wt% 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.

[0269] The obtained hydrogenated nitrile butadiene rubber was tested for its degree of hydrogenation 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%.

[0270] [Test Comparison Example 5]

[0271] Take 85g of SiO2 microsphere carrier (particle size 20μm, average pore size 110nm).

[0272] Take 5g of dimethyl dioctadecyl ammonium chloride, add 95g of o-xylene, and mix evenly with 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.

[0273] Infrared spectrum of surface-treated SiO2 support as shown in the figure Figure 4 As shown.

[0274] pass Figure 1 , Figures 3 to 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 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 Three 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 610-720 cm⁻¹ range. -1 There are no three characteristic peaks at 2840-2970 cm⁻¹. -1 There are also no three characteristic peaks at this location. The composite oxide support of the present invention 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.

[0275] As can be seen from Test Examples 1-27 and Comparative Examples 1-4, the present invention employs a method that works in synergy 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 supported catalyst and the easy separation and recovery of the catalyst.

[0276] 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 composite oxide carrier, characterized in that, include: SiO2 and group IVB metal oxides, wherein the group IVB metal oxides are TiO2 and / or ZrO2, and the surface properties of the composite oxide support are characterized by infrared spectra in the range of 610-720 cm⁻¹. -1 There are three characteristic peaks at 2840-2970 cm⁻¹. -1 There are three characteristic peaks at this point.

2. The composite oxide carrier according to claim 1, characterized in that, The surface properties of the composite oxide support are such that the infrared spectrum is within 620±1 cm⁻¹. -1 649±1cm -1 708±1cm -1 Characteristic peaks exist at [location]; and / or, the surface properties of the composite oxide support are such that the infrared spectrum is at 2850±1 cm⁻¹. -1 2919±1cm -1 2955±1cm -1 A characteristic peak exists at this location.

3. The composite oxide carrier according to claim 1, characterized in that, The composite oxide support is obtained by surface treatment of a composite oxide support precursor of SiO2 and group IVB metal oxides using an impregnation solution containing an organic cationic quaternary ammonium salt.

4. The composite oxide carrier according to claim 3, characterized in that, The surface treatment consists of impregnation and drying.

5. The composite oxide carrier according to claim 3, characterized in that, The organic cationic quaternary ammonium salt is a long-chain alkyl quaternary ammonium salt with more than 6 carbon atoms.

6. The composite oxide carrier according to claim 3, characterized in that, The organic cationic quaternary ammonium salt is a long-chain alkyl halogen quaternary ammonium salt with more than 6 carbon atoms.

7. The composite oxide carrier according to claim 3, 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.

8. The composite oxide support according to any one of claims 1-7, characterized in that, Based on the total weight of the composite oxide support, the content of group IVB metal oxide is 5–25 wt%, and the content of SiO2 is 75–95 wt%; and / or, the particle size of the composite oxide support is 5–30 μm; and / or, the average pore size is 100–1200 nm; and / or, the specific surface area is 30–200 m². 2 / g.

9. The composite oxide carrier according to claim 8, characterized in that, Based on the total weight of the composite oxide carrier, the content of group IVB metal oxides is 10–25 wt%, and the content of SiO2 is 75–90 wt%.

10. A method for preparing a composite oxide support according to any one of claims 1-9, characterized in that, Includes 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 oxide carrier precursor, wherein the group IVB metal compounds are titanium-containing compounds and / or zirconium-containing compounds. (2) The composite oxide carrier precursor is surface-treated with an impregnation solution containing organic cationic quaternary ammonium salt to obtain the composite oxide carrier.

11. The preparation method according to claim 10, 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.

12. The preparation method according to claim 11, characterized in that, In the impregnation solution containing the organic cationic quaternary ammonium salt, the concentration of the quaternary ammonium salt solution is 0.1–10 wt%.

13. The preparation method according to claim 11, characterized in that, The organic cationic quaternary ammonium salt is a long-chain alkyl quaternary ammonium salt with more than 6 carbons; and / or The solvent is selected from at least one of deionized water, methanol, ethanol, acetone, butanone, tetrahydrofuran, o-xylene, p-xylene, and pyridine; and / or The acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, and citric acid.

14. The preparation method according to claim 13, characterized in that, The organic cationic quaternary ammonium salt is a long-chain alkyl halogen quaternary ammonium salt with more than 6 carbon atoms.

15. The preparation method according to claim 13, 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.

16. The preparation method according to claim 13, characterized in that, The solvent is selected from at least one of o-xylene, p-xylene, and pyridine.

17. The preparation method according to claim 13, characterized in that, The solvent is o-xylene or pyridine.

18. The preparation method according to claim 13, characterized in that, The acid is hydrochloric acid.

19. The preparation method according to any one of claims 10-18, characterized in that, The surface treatment consists of impregnation and drying.

20. The preparation method according to claim 19, characterized in that, The impregnation conditions include a temperature of 20–60°C and a time of 0.5–8 h; the drying conditions include a temperature of 50–120°C and a time of 2–10 h.

21. The preparation method according to any one of claims 10-18, 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 ​​30–200 m². 2 / g.

22. The preparation method according to any one of claims 10-18, characterized in that, 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, in solutions containing titanium compounds and / or zirconium compounds, the concentration of the titanium compounds and / or zirconium compounds is 0.1 to 1.0 mol / L.

23. The preparation method according to any one of claims 10-18, characterized in that, The molar ratio of SiO2 microsphere carrier to group IVB metal compound is 3–40:1; and / or, the conditions for the first impregnation include: a temperature of 20–60°C and a time of 0.5–8 h; and / or, the conditions for the first drying include: a temperature of 105–130°C and a time of 2–8 h; and / or, the conditions for the first calcination include: a temperature of 450–650°C and a time of 3–8 h.

24. A supported catalyst, comprising: The composite oxide support according to any one of claims 1-9, and the active component Cu and its oxide supported on the support; the atomic cluster particle size of the active component copper is not greater than 5 nm; the content of Cu and its oxide, calculated as CuO, is 5 to 25 wt% based on the total weight of the supported catalyst.

25. The supported catalyst according to claim 24, characterized in that, The supported catalyst 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 ​​30–200 m². 2 / g; and / or, the atomic cluster particle size of the active component copper is 2–5 nm.

26. A method for preparing the supported catalyst according to claim 24 or 25, comprising the following steps: The composite oxide carrier according to any one of claims 1-9 or the composite oxide carrier obtained by the preparation method according to any one of claims 10-23 is subjected to a second impregnation with a solution of Cu soluble salt, followed by a second drying and a second calcination.

27. The preparation method according to claim 26, characterized in that, The molar ratio of the composite oxide support to the soluble salt of Cu is 1:0.03 to 0.6; and / or, the conditions for the second impregnation include: a temperature of 20 to 60°C and a time of 0.5 to 8 hours; and / or, the conditions for the second drying include: a temperature of 105 to 180°C and a time of 2 to 8 hours; and / or, the conditions for the second calcination include: a temperature of 450 to 650°C and a time of 3 to 8 hours.

28. The preparation method according to claim 26 or 27, characterized in that, The soluble salt of Cu is selected from at least one of copper chloride, copper sulfate, copper nitrate, copper acetate, and disodium ethylenediaminetetraacetate.

29. A catalyst composition comprising a homogeneous catalyst and the supported catalyst as described in claim 24 or 25.

30. The catalyst composition according to claim 29, characterized in that, The homogeneous catalyst comprises triphenylphosphine and triphenylphosphine chlorides of platinum group metals.

31. The catalyst composition according to claim 30, characterized in that, The triphenylphosphine chloride of the platinum group metal is triphenylphosphine rhodium chloride and / or triphenylphosphine ruthenium chloride.

32. The catalyst composition according to claim 30, characterized in that, The weight ratio of triphenylphosphine to triphenylphosphine chloride of platinum group metals is 2 to 5:

1.

33. The catalyst composition according to any one of claims 29-32, characterized in that, The weight ratio of the supported catalyst to the homogeneous catalyst is 1:0.01 to 0.

3.

34. A method for hydrogenating a polymer, comprising: The polymer is dissolved in an organic solvent, and then the catalyst composition according to any one of claims 29-33 is added to allow the polymer to react with hydrogen in the presence of the catalyst composition.

35. The hydrogenation method according to claim 34, characterized in that, The supported catalyst is used in an amount of 5 to 20 wt% of the polymer.

36. The hydrogenation method according to claim 34, characterized in that, The reaction conditions include: a temperature of 30–90°C, a hydrogen pressure of 5–10 MPa, and a time of 5–10 h.

37. The hydrogenation method according to any one of claims 34-36, characterized in that, The polymer is nitrile rubber.

38. The hydrogenation method according to any one of claims 34-36, characterized in that, The organic solvent is selected from at least one of chlorobenzene, acetone, butanone, tetrahydrofuran, dichloromethane, chloroform, cyclohexanone, ethyl acetate, and dimethylformamide.

39. The hydrogenated polymer obtained by the hydrogenation method according to any one of claims 34-38.

40. The hydrogenated polymer according to claim 39, characterized in that, The hydrogenated polymer is hydrogenated nitrile rubber.

41. The composite oxide support according to any one of claims 1-9, the composite oxide support obtained by the preparation method according to any one of claims 10-23, the supported catalyst according to claim 24 or 25, the supported catalyst obtained by the preparation method according to any one of claims 26-28, the catalyst composition according to any one of claims 29-33, the hydrogenated polymer obtained by the hydrogenation method of the polymer according to any one of claims 34-38, or the hydrogenated polymer according to claim 39 or 40, in the use of rubber products or in their manufacture.

42. The application according to claim 41, characterized in that, The application is in the field of hydrogenated nitrile rubber products or their manufacture.

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