Composite oxide carriers, supported catalysts, hydrogenated nitrile butadiene rubber, and methods for preparing and using the same.

Abstract

This invention discloses a composite oxide support, a supported catalyst, and a hydrogenated nitrile butadiene rubber, as well as a method for preparing the same and its use. The composite oxide support comprises SiO2 and a group IVB metal oxide, wherein the group IVB metal oxide is TiO2 and / or ZrO2, and the composite oxide support has an infrared spectrum of 610-720 cm⁻¹. -1 Three characteristic peaks exist within this range, and in the infrared spectrum, 2840-2970 cm⁻¹ -1 The surface properties include the presence of three other characteristic peaks within a certain range. The composite oxide support of the present invention can significantly improve the dispersibility of the active component on the catalyst surface and significantly enhance the hydrogenation activity of the catalyst. The supported catalyst of the present invention is used in combination with a homogeneous catalyst for hydrogenation saturation of polymer materials at low temperatures and pressures, and the resulting polymer (particularly hydrogenated nitrile butadiene rubber) product has a high degree of hydrogenation. Furthermore, the supported catalyst of the present invention can be reused multiple times, thereby improving the reusability of the catalyst and reducing preparation costs.

Description

Detailed description of the invention

[0001] [Technical field] The present invention relates to a composite oxide support and a method for preparing the same, a supported catalyst and a method for preparing the same, hydrogenated nitrile butadiene rubber, and a method for preparing the same and its applications.

[0002] [Background technology] Nitrile butadiene rubber (NBR) is a copolymer polymerized from acrylonitrile monomer and butadiene monomer, exhibiting excellent oil resistance, high abrasion resistance, good heat resistance, and strong adhesion. However, it has drawbacks such as poor cold resistance, poor odor resistance, poor insulation performance, and low elasticity. NBR is widely used in the manufacture of various oil-resistant rubber products in fields such as automotive, aerospace, and petroleum.

[0003] Hydrogenated nitrile butadiene rubber (HNBR) is a product obtained by catalytically selectively hydrogenating the unsaturated olefin moieties in the hydrocarbon chain of nitrile butadiene rubber (NBR). HNBR 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 industrial production method for HNBR is solution hydrogenation, which mainly includes homogeneous and heterogeneous hydrogenation. Homogeneous hydrogenation refers to the catalytic hydrogenation of polymers carried out under specific reaction conditions, with the active components of the catalyst dispersed in molecular form within the polymer solution. In homogeneous hydrogenation, the reactants and catalyst are uniformly mixed, the reaction conditions are easy to control, and the performance of the resulting product is stable. However, a common drawback of homogeneous solution hydrogenation is the difficulty in separating the catalyst from the product. Various techniques have been developed to address this problem. For example, ion exchange of precious metals using ion exchange resins, aqueous phase extraction and recovery of the precious metal rhodium using complexation of stannous chloride and rhodium catalyst, and the use of temperature-controlled phase transfer catalysts. However, with these methods, it is difficult to completely remove residual precious metal catalyst from the polymer, and there is a possibility of gel formation, affecting the quality of the product. Furthermore, the cost in large-scale industrialization is extremely high. Precious metal residues in the hydrogenation product increase production costs and waste precious metal resources. On the other hand, it accelerates the aging rate of HNBR and affects the machinability of the polymer.

[0005] Compared to homogeneous hydrogenation catalyst systems, heterogeneous catalytic reaction systems utilize precious metal-supported catalysts, effectively solving the problem of separating the catalyst from the hydrogenation product. This not only enables the reuse of the precious metal catalyst but also effectively avoids the residue of precious metals in the polymer. Currently, the preparation of supported catalysts still relies on conventional impregnation methods, which results in larger particle sizes of the active components and a significant reduction in the number of active centers. Furthermore, due to the weak interaction between the active components and the support, the precious metals are prone to detachment and loss from the support surface after vigorous stirring reactions. This reduces the effectiveness of the catalyst and affects the performance of the hydrogenation product. Zeon Corporation uses SiO2 as a support for Pd metal for the hydrogenation of NBR, achieving a hydrogenation degree of over 95% in a single pass. However, the catalyst's performance deteriorates with repeated use. For example, activity begins to decrease from the second use, and by the third to fourth use, activity drops significantly, resulting in a substantial decrease in the hydrogenation degree.

[0006] Homogeneous catalytic hydrogenation achieves a high degree of hydrogenation, but catalyst separation is difficult, leading to increased costs. Heterogeneous catalytic hydrogenation for polymer saturation does not achieve a sufficiently high degree of hydrogenation. Furthermore, there is a loss of active components during the reactor stirring process, or the effectiveness of the catalyst decreases significantly with repeated use, resulting in a substantial reduction in the degree of hydrogenation. Therefore, there is a need to develop catalysts and related usage methods that guarantee a high degree of hydrogenation, facilitate catalyst separation and recovery, and ensure the repeated use of heterogeneous catalysts.

[0007] Currently, all of the catalysts mentioned above use precious metals such as rhodium, palladium, ruthenium, osmium, platinum, and iridium as active ingredients. The prior art does not disclose any heterogeneous supported catalysts for NBR that use non-precious metals as active ingredients while simultaneously possessing high activity, high selectivity, and high stability.

[0008] [Information content] To address the aforementioned problems in the prior art, the present invention provides a novel composite oxide support. This composite oxide support has an infrared (IR) spectrum of 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1The surface exhibits three characteristic peaks within a certain range. This support significantly improves the dispersibility of the active component on the catalyst surface and allows the atomic cluster size of the active component to be controlled to 5 nm or less, thereby dramatically improving the hydrogenation activity of the catalyst. Furthermore, the novel multifunctional non-precious metal supported catalyst of the present invention uses SiO2 microspheres as a support and non-precious metals as the main active component, resulting in small particle size. By employing a synergistic cooperative method with a homogeneous catalyst, the present invention ensures hydrogenation saturation of the polymer material under relatively low temperatures and pressures, and the resulting hydrogenated polymer product (e.g., HNBR) achieves a high degree of hydrogenation. Moreover, the supported catalyst of the present invention can be reused multiple times, and the catalyst composition can be easily separated and recovered. In particular, by using non-precious metals as the active component for preparing the supported catalyst, the problem of loss of precious metal active components is avoided, further improving the recoverability of the catalyst and significantly reducing catalyst costs. This reduces the manufacturing cost of hydrogenated polymers (e.g., HNBR).

[0009] A first aspect of the present invention provides a composite oxide support characterized by comprising SiO2 and a group IVB metal oxide, wherein the group IVB metal oxide is TiO2 and / or ZrO2, and the composite oxide support has an infrared (IR) spectrum of 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1 The surface exhibits three characteristic peaks within a certain range. The infrared spectral measurement conditions in this invention are as follows: A Nicolet iS50 infrared spectrometer is used; sample preparation and scanning are performed in attenuated total reflection mode; the scanning range is 4000-400 cm. -1 Let's set the resolution to 4cm. -1 The number of scans is set to 32. For example, as shown in Figure 1, the composite oxide support according to the present invention has an infrared spectrum of 610-720 cm⁻¹. -1 Three characteristic peaks are observed within the range of 2840-2970 cm². -1 It has surface properties that exhibit three characteristic peaks within a certain range.

[0010] In some embodiments of the composite oxide support according to the present invention, the infrared spectrum of the composite oxide support shows three characteristic peaks in the range of 620 to 710 cm -1 and has a surface property of showing three characteristic peaks in the range of 2850 to 2960 cm -1 .

[0011] In some embodiments of the composite oxide support according to the present invention, the infrared spectrum of the composite oxide support has a surface property of showing characteristic peaks at 620 ± 1 cm -1 , 649 ± 1 cm -1 , and 708 ± 1 cm -1 ; and / or the composite oxide support has a surface property of showing characteristic peaks at 2850 ± 1 cm -1 , 2919 ± 1 cm -1 , and 2955 ± 1 cm -1 .

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

[0013] In some embodiments of the composite oxide support according to the present invention, the organic cationic quaternary ammonium salt is a long-chain alkyl quaternary ammonium salt having C6 or more (C6+), preferably a halogenated C6+ long-chain alkyl quaternary ammonium salt. Preferably, the halogen is Cl, Br, or I, and Cl is more preferable. More preferably, the C6+ long-chain alkyl group is a C6-C 24 alkyl group, more preferably a C8-C 22 alkyl group, still more preferably a C 10 ]>-C 20 alkyl group, even more preferably a C 12 -C 18It is an alkyl group. More preferably, the organic cationic quaternary ammonium salt is dimethyldioctadecylammonium chloride, cetyltrimethylammonium chloride, and C chloride. 12-14 - At least one selected from alkyldimethylethylbenzylammonium.

[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 surface treatment process of the composite oxide support precursor using the organic cationic quaternary ammonium salt does not include any high-temperature treatment steps (e.g., temperatures above 300°C) such as roasting, firing, or sintering. In the infrared spectrum of the composite oxide support according to the present invention, the 610-720 cm⁻¹ range is -1 Three characteristic peaks within this range, for example, 620-710 cm² -1 Three characteristic peaks within the range of 620±1cm -1 , 649±1cm -1 , 708±1cm -1 The characteristic peaks in this region are mainly due to C-halogen (e.g., C-Cl) vibrations. -1 Three characteristic peaks within the range, for example, 2850-2960 cm. -1 Three characteristic peaks within the range of 2850±1cm -1 , 2919±1cm -1 , 2955±1cm -1 The characteristic peaks in this case are mainly due to CH oscillations.

[0015] In some embodiments of the method for preparing a composite oxide support according to the present invention, the content of the group IVB metal oxide is 5 to 25% by weight and the content of SiO2 is 75 to 95% by weight, based on the total weight of the composite oxide support. For example, the content of the group IVB metal oxide may be 5 to 20% by weight, 5 to 15% by weight, 5 to 10% by weight, 10 to 25% by weight, 10 to 20% by weight, 10 to 15% by weight, 12 to 25% by weight, 12 to 20% by weight, 12 to 15% by weight, 15 to 25% by weight, 15 to 20% by weight, 20 to 25% by weight, etc., but is not limited to these. Correspondingly, the SiO2 content is 80-95% by weight, 85-95% by weight, 90-95% by weight, 75-90% by weight, 80-90% by weight, 85-90% by weight, 75-88% by weight, 80-88% by weight, 85-88% by weight, 75-85% by weight, 80-85% by weight, 75-80% by weight, etc. Preferably, the content of the group IVB metal oxide is 10-25% by weight, and the SiO2 content is 75-90% by weight. Preferably, the content of the group IVB metal oxide is more than 10% by weight and 25% by weight, and the SiO2 content is 75% by weight and less than 90% by weight. Preferably, the content of the group IVB metal oxide is 11-25% by weight, and the SiO2 content is 75-89% by weight. Preferably, the content of the group IVB metal oxide is 12 to 25% by weight, and the content of SiO2 is 75 to 88% by weight. Preferably, the content of the group IVB metal oxide is 15 to 25% by weight, and the content of SiO2 is 75 to 85% by weight.

[0016] In some embodiments of the method for preparing a composite oxide support according to the present invention, when the IVB group metal oxides are TiO2 and ZrO2, the ratio of TiO2 to ZrO2 can vary within a wide range. For example, 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, and 0.5-1:1, but is not limited to these.

[0017] In some embodiments of the method for preparing a composite oxide support according to the present invention, the particle size of the composite oxide support is 5 to 30 μm. For example, this includes, but is not limited to, ranges between any two of the above values, such as 5 to 25 μm, 5 to 20 μm, 5 to 15 μm, 5 to 10 μm, 10 to 30 μm, 10 to 25 μm, 10 to 20 μm, 10 to 15 μm, 15 to 30 μm, 15 to 25 μm, 15 to 20 μm, 20 to 30 μm, and 20 to 25 μm. In the present invention, the particle size of the composite oxide support is measured using a Malvern MS2000 laser particle size analyzer in accordance with the test method specified in NB / SH / T 0951-2017.

[0018] In some embodiments of the method for preparing a composite oxide support according to the present invention, the average pore diameter of the composite oxide support is 100 to 1200 nm. For example, 100 to 1000 nm, 100 to 800 nm, 100 to 600 nm, 100 to 500 nm, 100 to 400 nm, 100 to 300 nm, 100 to 200 nm, 200 to 1200 nm, 200 to 1000 nm, 200 to 800 nm, 200 to 600 nm, 200 to 500 nm, 200 to 400 nm, 200 to 400 nm, 300 to 1200 nm, 300 to 1000 nm, 300 to 800 nm, 300 to 600 nm, 300 to 500 nm, 300 to 400 nm, 400 to 1200 nm, 400 to 1000 nm, 400 Examples include 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., and include, but are not limited to, the range between any two of the aforementioned values. In the present invention, the average pore size of the composite oxide support is measured using an AutoPore IV 9500 high-performance fully automated mercury porosimetry meter manufactured by Micromeritics Instrument Corporation (USA), in accordance with the mercury intrusion porosimetry method specified in GB / T 21650.1-2008 (Measurement of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption method - Part 1: Mercury intrusion porosimetry method).

[0019] In some embodiments of the method for preparing a composite oxide support according to the present invention, the specific surface area of ​​the composite oxide support is 30 to 200 m². 2 It is / g. For example, 30-150m 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 Examples include / g, and include, but are not limited to, the range between any two of the aforementioned values. In the present invention, the specific surface area of ​​the composite oxide support is measured using an AutoPore IV 9500 high-performance fully automatic mercury porosimetry meter manufactured by Micromeristics Instrument Corporation (USA), in accordance with the mercury intrusion porosimetry method specified in GB / T 21650.1-2008 (Measurement of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption method - Part 1: Mercury intrusion porosimetry method).

[0020] A second aspect of the present invention provides a method for preparing the aforementioned composite oxide support, the method comprising the following steps: (1) A step of obtaining a composite oxide carrier precursor by subjecting an SiO2 microsphere carrier to a first impregnation using a solution of a group IVB metal compound, followed by a first drying and a first roasting, wherein the group IVB metal compound is a titanium-containing compound and / or a zirconium-containing compound; (2) A step of surface-treating the composite oxide support precursor with an impregnation solution containing an organic cationic quaternary ammonium salt to obtain a composite oxide support.

[0021] In some embodiments of the method for preparing a composite oxide support according to the present invention, the impregnation solution containing the organic cationic quaternary ammonium salt comprises the organic cationic quaternary ammonium salt, a solvent, and an acid.

[0022] In some embodiments of the method for preparing a composite oxide support according to the present invention, the organic cationic quaternary ammonium salt is a C6+ long-chain alkyl quaternary ammonium salt, preferably a halogenated C6+ long-chain alkyl quaternary ammonium salt. Preferably, the halogen is Cl, Br, or I, with Cl being more preferred. More preferably, the C6+ long-chain alkyl group is C6-C 24 It is an alkyl group, more preferably C8-C 22 Alkyl alkyl groups, more preferably C 10 -C 20 Alkyl alkyl groups, more preferably C 12 -C 18 It is an alkyl group. More preferably, the organic cationic quaternary ammonium salt is dimethyldioctadecylammonium chloride, cetyltrimethylammonium chloride, and C chloride. 12-14 - At least one selected from alkyldimethylethylbenzylammonium.

[0023] In some embodiments of the method for preparing a composite oxide support according to the present invention, the solvent is at least one selected from deionized water, methanol, ethanol, acetone, methyl ethyl ketone, tetrahydrofuran, o-xylene, p-xylene, and pyridine. Preferably, the solvent is at least one selected from o-xylene, p-xylene, and pyridine. More preferably, the solvent is o-xylene or pyridine.

[0024] In some embodiments of the method for preparing a composite oxide support according to the present invention, the acid is at least one selected from 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% by weight.

[0025] In some embodiments of the method for preparing a composite oxide support according to the present invention, the concentration of the quaternary ammonium salt in the impregnation solution containing the organic cationic quaternary ammonium salt is 0.1 to 10% by weight. More preferably, the weight ratio of the organic cationic quaternary ammonium salt, solvent, and acid is 1:10 to 19:1 to 3. For example, the weight of 1 mL of 37% by weight concentrated hydrochloric acid in the examples is 1.18 g.

[0026] In some embodiments of the method for preparing a composite oxide support according to the present invention, the surface treatment is impregnation and drying. Preferably, the impregnation conditions are a temperature of 20 to 60°C and a time of 0.5 to 8 hours. The drying conditions are a temperature of 50 to 120°C and a time of 2 to 10 hours. The entire surface treatment process of the composite oxide support precursor using the organic cationic quaternary ammonium salt does not include any high-temperature treatment steps (e.g., temperatures above 300°C) such as roasting, calcination, or sintering. Therefore, the groups of the organic cationic quaternary ammonium salt and acid (e.g., amino groups, hydrogen ions, halide ions, alkyl groups, etc.) can be retained on the composite oxide support, and these groups can interact with the active ingredient, thereby promoting the dispersion of the active ingredient.

[0027] In the present invention, a composite oxide support of SiO2 containing TiO2 and / or ZrO2 can be obtained by simultaneously impregnating the SiO2 microsphere support with a solution of a titanium-containing compound and / or a zirconium-containing compound, followed by drying and roasting. Alternatively, a composite oxide support of SiO2 containing TiO2 and / or ZrO2 can be obtained by first impregnating the SiO2 microsphere support with a solution of a titanium-containing compound, then drying and roasting, followed by impregnation with a solution of a zirconium-containing compound, followed by drying and roasting. Alternatively, a composite oxide support of SiO2 containing TiO2 and / or ZrO2 can be obtained by first impregnating the SiO2 microsphere support with a solution of a zirconium-containing compound, then drying and roasting, followed by impregnation with a solution of a titanium-containing compound, followed by drying and roasting.

[0028] In some embodiments of the method for preparing a composite oxide support according to the present invention, the particle size of the SiO2 microsphere support is 5 to 30 μm. For example, this includes, but is not limited to, ranges between any two of the above values, such as 5 to 25 μm, 5 to 20 μm, 5 to 15 μm, 5 to 10 μm, 10 to 30 μm, 10 to 25 μm, 10 to 20 μm, 10 to 15 μm, 15 to 30 μm, 15 to 25 μm, 15 to 20 μm, 20 to 30 μm, and 20 to 25 μm. In the present invention, the particle size of the SiO2 microsphere support is measured using a Malvern MS2000 laser particle size analyzer in accordance with the test method specified in NB / SH / T 0951-2017.

[0029] In some embodiments of the method for preparing a composite oxide support according to the present invention, the average pore size of the SiO2 microsphere support is 100 to 1200 nm. For example, 100 to 1000 nm, 100 to 800 nm, 100 to 600 nm, 100 to 500 nm, 100 to 400 nm, 100 to 300 nm, 100 to 200 nm, 200 to 1200 nm, 200 to 1000 nm, 200 to 800 nm, 200 to 600 nm, 200 to 500 nm, 200 to 400 nm, 200 to 400 nm, 300 to 1200 nm, 300 to 1000 nm, 300 to 800 nm, 300 to 600 nm, 300 to 500 nm, 300 to 400 nm, 400 to 1200 nm, 400 to 1000 nm, 400 Examples include 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., and include, but are not limited to, the range between any two of the aforementioned values. In the present invention, the average pore size of the SiO2 microsphere carrier is measured using the AutoPore IV 9500 high-performance fully automated mercury porosimetry meter manufactured by Micromeristics Instrument Corporation (USA), in accordance with the mercury intrusion porosimetry method specified in GB / T 21650.1-2008 (Measurement of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption method - Part 1: Mercury intrusion porosimetry method).

[0030] In some embodiments of the method for preparing a composite oxide support according to the present invention, the specific surface area of ​​the SiO2 microsphere support is 30 to 200 m². 2 It is / g. For example, 30-150m 2 / g, 30-120m 2 / g, 30-100m 2 / g, 30-90m 2 / g, 30-80m 2 / g, 30-70m 2 / g, 30-60m2 / g, 30 - 50 m 2 / g, 30 - 40 m 2 / g, 50 - 200 m 2 / g, 50 - 150 m 2 / g, 50 - 120 m 2 / g, 50 - 100 m 2 / g, 50 - 90 m 2 / g, 50 - 80 m 2 / g, 50 - 70 m 2 / g, 50 - 60 m 2 / g, 80 - 200 m 2 / g, 80 - 150 m 2 / g, 80 - 120 m 2 / g, 80 - 100 m 2 / g, 80 - 90 m 2 / g, 100 - 200 m 2 / g, 100 - 150 m 2 / g, 100 - 120 m 2 / g, 120 - 200 m 2 / g, 120 - 150 m 2 Examples include / g, etc., including ranges between any two of the above values, but not limited thereto. In the present invention, the specific surface area of the SiO2 microsphere carrier is measured using an AutoPore IV 9500 high-performance fully automatic mercury porosimeter manufactured by Micromeritics Instrument Corporation (USA) in accordance with the mercury intrusion porosimetry method specified in GB / T 21650.1 - 2008 (Measurement of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption method - Part 1: Mercury intrusion porosimetry method).

[0031] In some embodiments of the method for preparing the composite oxide carrier according to the present invention, the composite oxide treated with the quaternary ammonium salt has an infrared spectrum showing three characteristic peaks in the range of 610 - 720 cm -1 and having a surface characteristic of showing three characteristic peaks in the range of 2840 - 2970 cm -1 The infrared spectrum measurement can be performed under the following conditions: using a Nicolet iS50 infrared spectrometer; performing sample preparation and scanning in the attenuated total reflection mode; setting the scanning range from 4000 - 400 cm-1 Let's set the resolution to 4cm. -1 Let's assume the number of scans is 32.

[0032] In the present invention, the SiO2 microsphere carrier may be a commercially available product (for example, manufactured by Shandong Bangkai Materials Co., Ltd., J&K Scientific, Shanghai Aladdin Biochemical Technology Co., Ltd., etc.) or may be a self-made product.

[0033] In some embodiments of the method for preparing a composite oxide support according to the present invention, the titanium-containing compound is at least one selected from titanium sulfate, metatitanic acid, titanium tetrachloride, and tetrabutyl titanate. For example, titanium sulfate and titanium tetrachloride can be dissolved in water. Metatitanic acid can be dissolved in a dilute sulfuric acid solution. Alternatively, tetrabutyl titanate can be dissolved in an ethanol solution.

[0034] In some embodiments of the method for preparing a composite oxide support according to the present invention, the zirconium-containing compound is at least one selected from zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconyl chloride, and zirconium oxalate. For example, the aforementioned zirconium compounds can be dissolved in water.

[0035] In some embodiments of the method for preparing a composite oxide support according to the present invention, the concentration of the titanium-containing compound and / or zirconium-containing compound in the solution of the titanium-containing compound and / or zirconium-containing compound is 0.1 to 1.0 mol / L. For example, ranges such as 0.1~0.8 mol / L, 0.1~0.6 mol / L, 0.1~0.4 mol / L, 0.2~1.0 mol / L, 0.2~0.8 mol / L, 0.2~0.6 mol / L, 0.2~0.4 mol / L, 0.3~1.0 mol / L, 0.3~0.8 mol / L, 0.3~0.6 mol / L, 0.3~0.4 mol / L, 0.4~1.0 mol / L, 0.4~0.8 mol / L, 0.4~0.6 mol / L, 0.5~1.0 mol / L, 0.5~0.8 mol / L, 0.5~0.6 mol / L, etc., include, but are not limited to, any range between any two of the aforementioned values.

[0036] In some embodiments of the method for preparing a composite oxide support according to the present invention, the molar ratio of the SiO2 microsphere support to the group IVB metal-containing compound is 3 to 40:1, for example, 4 to 26:1, 5 to 30:1, or 6 to 39:1. Here, the amount of the SiO2 microsphere support is calculated as Si, and the amounts of the titanium-containing compound and / or zirconium-containing compound are calculated as titanium and / or zirconium elements.

[0037] In some embodiments of the method for preparing a composite oxide support according to the present invention, the first impregnation conditions are a temperature of 20 to 60°C and a time of 0.5 to 8 hours.

[0038] In some embodiments of the method for preparing a composite oxide support according to the present invention, the first drying conditions are a temperature of 105 to 130°C and a time of 2 to 8 hours.

[0039] In some embodiments of the method for preparing a composite oxide support according to the present invention, the first roasting conditions are a temperature of 450 to 650°C and a time of 3 to 8 hours.

[0040] A third aspect of the present invention is to provide a supported catalyst comprising the aforementioned composite oxide support and Cu and its oxides as active components supported on the support; the particle size of the copper atom clusters of the active components is 5 nm or less; and the content of Cu and its oxides in terms of CuO, based on the total weight of the supported catalyst, is 5 to 25% by weight, preferably 8 to 25% by weight, more preferably 10 to 25% by weight, and even more preferably 12 to 25% by weight.

[0041] In some embodiments of the supported catalyst according to the present invention, the particle size of the supported catalyst is 5 to 30 μm. For example, this includes, but is not limited to, ranges between any two of the above values, such as 5 to 25 μm, 5 to 20 μm, 5 to 15 μm, 5 to 10 μm, 10 to 30 μm, 10 to 25 μm, 10 to 20 μm, 10 to 15 μm, 15 to 30 μm, 15 to 25 μm, 15 to 20 μm, 20 to 30 μm, and 20 to 25 μm. In the present invention, the particle size of the catalyst is measured using a Malvern MS2000 laser particle size analyzer in accordance with the test method specified in NB / SH / T 0951-2017.

[0042] In some embodiments of the supported catalyst according to the present invention, the average pore size of the supported catalyst is 100 to 1200 nm. For example, 100 to 1000 nm, 100 to 800 nm, 100 to 600 nm, 100 to 500 nm, 100 to 400 nm, 100 to 300 nm, 100 to 200 nm, 200 to 1200 nm, 200 to 1000 nm, 200 to 800 nm, 200 to 600 nm, 200 to 500 nm, 200 to 400 nm, 200 to 400 nm, 300 to 1200 nm, 300 to 1000 nm, 300 to 800 nm, 300 to 600 nm, 300 to 500 nm, 300 to 400 nm, 400 to 1200 nm, 400 to 1000 nm, 400 Examples include 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., and include, but are not limited to, the range between any two of the aforementioned values. In this invention, the average pore size of the catalyst is measured using an AutoPore IV 9500 high-performance fully automated mercury porosimetry meter manufactured by Micromeristics Instrument Corporation (USA), in accordance with the mercury intrusion porosimetry method specified in GB / T 21650.1-2008 (Measurement of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption method - Part 1: Mercury intrusion porosimetry method).

[0043] In some embodiments of the supported catalyst according to the present invention, the specific surface area of ​​the supported catalyst is 30 to 200 m². 2 It is / g. For example, 30-150m 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 Examples include / g, and include, but are not limited to, the range between any two of the aforementioned values. In the present invention, the specific surface area of ​​the catalyst is measured using an AutoPore IV 9500 high-performance fully automatic mercury porosimetry meter manufactured by Micromeristics Instrument Corporation (USA), in accordance with the mercury intrusion porosimetry method specified in GB / T 21650.1-2008 (Measurement of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption method - Part 1: Mercury intrusion porosimetry method).

[0044] In some embodiments of the supported catalyst according to the present invention, the particle size of the copper atom clusters of the active component is 2 to 5 nm, which is characterized by transmission electron microscopy (TEM) and measured based on a scale bar.

[0045] In some embodiments of the supported catalyst according to the present invention, the supported catalyst is substantially free of precious metals such as rhodium, palladium, ruthenium, osmium, platinum, and iridium. The expression "substantially free" means that the content of precious metals (e.g., rhodium, palladium, ruthenium, osmium, platinum, and iridium) in the supported catalyst is less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0.2% by weight, preferably less than 0.1% by weight, and preferably 0% by weight. Preferably, the supported catalyst is completely free of precious metals such as rhodium, palladium, ruthenium, osmium, platinum, and iridium.

[0046] In some embodiments of the supported catalyst according to 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 expression "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% by weight, preferably less than 0.5% by weight, preferably less than 0.2% by weight, preferably less than 0.1% by weight, and preferably 0% by weight. 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).

[0047] In some embodiments of the supported catalyst according to the present invention, the supported catalyst is substantially free of metals other than copper, titanium, and zirconium. The expression "substantially free" means that the content of metals other than copper, titanium, and zirconium in the supported catalyst is less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0.2% by weight, preferably less than 0.1% by weight, and preferably 0% by weight. Preferably, the supported catalyst is completely free of metals other than copper, titanium, and zirconium.

[0048] A fourth aspect of the present invention provides a method for preparing the aforementioned supported catalyst, the method comprising the following steps: subjecting the aforementioned composite oxide support to a second impregnation with a solution of a soluble copper salt, followed by a second drying and a second roasting.

[0049] In some embodiments of the method for preparing a supported catalyst according to the present invention, the molar ratio of the composite oxide support to the soluble copper salt 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 calculated as Si, and the soluble copper salt is calculated as element Cu.

[0050] In some embodiments of the method for preparing a supported catalyst according to the present invention, the soluble copper salt is at least one selected from copper chloride, copper sulfate, copper nitrate, copper acetate, and disodium copper ethylenediaminetetraacetate (EDTA-Cu-15).

[0051] In some embodiments of the method for preparing a supported catalyst according to the present invention, the second impregnation conditions are a temperature of 20 to 60°C and a time of 0.5 to 8 hours.

[0052] In some embodiments of the method for preparing a supported catalyst according to the present invention, the second drying conditions are a temperature of 105 to 180°C and a time of 2 to 8 hours.

[0053] In some embodiments of the method for preparing a supported catalyst according to the present invention, the conditions for the second roasting are a temperature of 450 to 650°C and a time of 3 to 8 hours.

[0054] In some embodiments of the method for preparing a supported catalyst according to the present invention, the amounts of the SiO2 microsphere support and the titanium-containing compound solution are set such that, based on the total weight of the prepared composite oxide support of SiO2 with TiO2 and / or ZrO2, the TiO2 and / or ZrO2 content is 5 to 25% by weight and the SiO2 content is 75 to 95% by weight.

[0055] In some embodiments of the method for preparing a supported catalyst according to the present invention, the amount of soluble copper salt used for the second impregnation of the SiO2 composite oxide support with TiO2 and / or ZrO2 is set such that the CuO content, in terms of CuO, is 5 to 25% by weight, based on the total weight of the supported catalyst. For example, these amounts may be 5 to 20% by weight, 5 to 15% by weight, 5 to 10% by weight, 10 to 25% by weight, 10 to 20% by weight, 10 to 15% by weight, 12 to 25% by weight, 12 to 20% by weight, 12 to 15% by weight, 15 to 25% by weight, 15 to 20% by weight, 20 to 25% by weight, etc., but are not limited to these.

[0056] A fifth aspect of the present invention is to provide a catalyst composition comprising a homogeneous catalyst and the aforementioned supported catalyst.

[0057] In some embodiments of the catalyst composition according to the present invention, any homogeneous catalyst commonly used in the art can be employed. Examples include transition metal ruthenium carbene complexes, Grubbs catalysts (e.g., catalysts for olefin metathesis), triphenylphosphine, and platinum group metal triphenylphosphine chlorides. Preferably, the homogeneous catalyst comprises triphenylphosphine and platinum group metal triphenylphosphine chloride.

[0058] Specifically, transition metal ruthenium carbene complex catalysts include, but are not limited to, structures represented by the following formulas (1) to (7):

[0059] [ka]

[0060] The structure of the aforementioned Grubbs catalyst includes, but is not limited to, that represented by formula (8):

[0061] [ka]

[0062] In some embodiments of the hydrogenation method for HNBR according to the present invention, the platinum group metal triphenylphosphine chloride is rhodium triphenylphosphine chloride and / or ruthenium triphenylphosphine chloride.

[0063] In some embodiments of the HNBR hydrogenation method according to the present invention, the weight ratio of triphenylphosphine to the platinum group metal triphenylphosphine chloride is 2 to 5:1. Examples include, but are not limited to, 2 to 5:1, 2 to 4:1, and 2 to 3:1.

[0064] In some embodiments of the HNBR hydrogenation method according to the present invention, the weight ratio of the supported catalyst to the homogeneous catalyst is 1:0.01 to 0.3. Examples include, but are not limited to, 1:0.05 to 0.3, 1:0.1 to 0.3, 1:0.15 to 0.3, and 1:0.16 to 0.3.

[0065] A sixth aspect of the present invention provides a method for hydrogenating a polymer, the method comprising dissolving the polymer in an organic solvent, then adding the catalyst composition, and reacting the polymer with hydrogen in the presence of the catalyst composition. The hydrogenation method is usually carried out in a reactor. In this method, the polymer dissolved in the organic solvent is first added to the reactor, then the catalyst composition is added, the reactor is then closed, hydrogen is introduced and air is replaced, and the polymer reacts with hydrogen in the presence of the catalyst composition.

[0066] In some embodiments of the polymer hydrogenation method according to the present invention, the amount of the supported catalyst accounts for 5 to 20% by weight of the polymer, for example, 5 to 20% by weight, 5 to 15% by weight, 5 to 10% by weight, 10 to 20% by weight, 10 to 15% by weight, 15 to 20% by weight, and so on.

[0067] In some embodiments of the polymer hydrogenation method according to the present invention, the reaction conditions are a temperature of 30 to 90°C, a hydrogen pressure of 5 to 10 MPa, and a duration of 5 to 10 hours.

[0068] In some embodiments of the polymer hydrogenation method according to the present invention, the amount of organic solvent used to dissolve the polymer is such that the polymer content in the organic solvent is 0.1 to 10% by weight, based on the total weight of the polymer and the solvent, for example, 0.1 to 10% by weight, 0.1 to 8% by weight, 0.1 to 6% by weight, 0.1 to 4% by weight, 0.1 to 2% by weight, 0.1 to 1% by weight, These include 0.5-10% by weight, 0.5-8% by weight, 0.5-6% by weight, 0.5-4% by weight, 0.5-2% by weight, 0.5-1% by weight, 1-10% by weight, 1-8% by weight, 1-6% by weight, 1-4% by weight, 1-2% by weight, 3-10% by weight, 3-8% by weight, 3-6% by weight, 3-4% by weight, 5-10% by weight, 5-8% by weight, 5-6% by weight, 7-10% by weight, 7-8% by weight, 8-10% by weight, 9-10% by weight, and so on.

[0069] In some embodiments of the polymer hydrogenation method according to the present invention, the polymer is an unsaturated copolymer of a conjugated diene and a copolymerizable monomer. The conjugated diene is at least one selected from butadiene, isoprene, piperine, and 2,3-dimethylbutadiene, preferably butadiene and / or isoprene, and more preferably butadiene. The copolymerizable monomer is at least one selected from acrylonitrile, methacrylonitrile, styrene, propyl acrylate, butyl acrylate, propyl methacrylate, and butyl methacrylate, preferably acrylonitrile and / or methacrylonitrile, and more preferably acrylonitrile.

[0070] In some embodiments of the polymer hydrogenation method according to the present invention, the polymer is NBR. In the art, NBR refers to a copolymer polymerized from an acrylonitrile monomer and a butadiene monomer.

[0071] In some embodiments of the polymer hydrogenation method according to the present invention, there are no particular restrictions on the type of NBR, that is, the hydrogenation method of the present invention can be used for hydrogenating almost all types of NBR. For example, NBR can be obtained commercially (e.g., from Zeon, in grades such as the 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 from Qilu Petrochem.) or can be manufactured in-house.

[0072] For example, the acrylonitrile content of the NBR may be 15-55% by weight, for example, 19-51% by weight, 20-55% by weight, 25-55% by weight, 30-55% by weight, 35-55% by weight, 40-55% by weight, 45-55% by weight, 20-50% by weight, 25-50% by weight, 30-50% by weight, 35-50% by weight, 40-50% by weight, 45-50% by weight, 2 Examples include 0-45% by weight, 25-45% by weight, 30-45% by weight, 35-45% by weight, 40-45% by weight, 20-40% by weight, 25-40% by weight, 30-40% by weight, 35-40% by weight, 20-35% by weight, 25-35% by weight, 30-35% by weight, 20-25% by weight, 20-30% by weight, and 25-30% by weight, and include the range between any two of the aforementioned values.

[0073] For example, the Mooney viscosity (ML, 100℃, 1+4) of the NBR may be between 20 and 100, and examples include 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, and 90-100, including the range between any two of the aforementioned values.

[0074] In some embodiments of the polymer hydrogenation method according to the present invention, the organic solvent is at least one selected from chlorobenzene, acetone, methyl ethyl ketone, tetrahydrofuran, dichloromethane, chloroform, cyclohexanone, ethyl acetate, and dimethylformamide.

[0075] In some embodiments of the polymer hydrogenation method according to the present invention, the polymer hydrogenation method further includes recovering the supported catalyst by filtration or centrifugation after the reaction is complete, and recovering the homogeneous catalyst by ion exchange using an ion exchange resin.

[0076] In some embodiments of the polymer hydrogenation method according to the present invention, the degree of hydrogenation is at least 90%. Examples include, but are 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 degree of hydrogenation is measured according to SH / T 1762-2008 / ISO 14558:2000.

[0077] In some embodiments of the polymer hydrogenation method according to the present invention, the selectivity is at least 98%. Examples include, but are 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 measured by infrared spectroscopy using a Nicolet 560 FTIR spectrometer from Nicolet Instruments, Inc. (USA).

[0078] A seventh aspect of the present invention is to provide a hydrogenated polymer, preferably HNBR, obtained by the hydrogenation method described above.

[0079] In some embodiments of the hydrogenated polymer, preferably HNBR, according to the present invention, the degree of hydrogenation of the hydrogenated polymer, preferably HNBR, is at least 90%. Examples include, but are 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 degree of hydrogenation is measured according to SH / T 1762-2008 / ISO 14558:2000.

[0080] In some embodiments of the HNBR according to the present invention, the HNBR exhibits excellent properties such as good oil resistance, heat resistance, chemical corrosion resistance, and odor resistance, as well as high tear resistance and abrasion resistance.

[0081] An eighth aspect of the present invention is to provide the use of the above-mentioned composite oxide carrier, the composite oxide carrier obtained by the above-mentioned method for preparing the composite oxide carrier, the above-mentioned supported catalyst, the supported catalyst obtained by the above-mentioned method for preparing the supported catalyst, the above-mentioned catalyst composition, the hydrogenated polymer obtained by the above-mentioned hydrogenation method, or the above-mentioned hydrogenated polymer in the manufacture of rubber products or the manufacture of HNBR products or the manufacture of the above-mentioned products.

[0082] Advantages of the present invention: (1) By modifying a composite support of SiO2 and a group IVB metal oxide with an impregnation solution containing an organic cationic quaternary ammonium salt, the dispersibility of the active component on the catalyst surface can be significantly improved, and the Cu atom cluster size of the active component can be controlled to 5 nm or less. This significantly improves the hydrogenation activity of the catalyst.

[0083] (2) Supported catalysts prepared based on a composite support of SiO2 treated with an organic cationic quaternary ammonium salt and a group IVB metal oxide have a pore structure suitable for the hydrogenation of macromolecules such as NBR. TiO2 and / or ZrO2 on the support surface can improve the hydrogenation activity of the catalyst, and the catalyst exhibits good hydrogenation activity and stability.

[0084] (3) The synergistic cooperation between the supported catalyst and the homogeneous catalyst of the present invention enables hydrogenation saturation of the polymer material at relatively low temperatures and pressures, and the resulting hydrogenated polymer (e.g., HNBR) product achieves a high degree of hydrogenation.

[0085] (4) After the reaction is complete, the supported catalyst is recovered by filtration or centrifugation, and the homogeneous catalyst is recovered by ion exchange using an ion exchange resin. This ensures that the supported catalyst can be reused multiple times and facilitates the separation and recovery of the catalyst.

[0086] (5) By using the supported catalyst and hydrogenation method for hydrogenated polymer (e.g., HNBR) according to the present invention, a supported catalyst for hydrogenation of NBR with a non-precious metal as the active component can be prepared for the first time. This avoids the problem of loss of the precious metal active component, further improves the recoverability of the catalyst, and significantly reduces the catalyst cost. This reduces the manufacturing cost of the hydrogenated polymer (HNBR).

[0087] [Brief description of the drawing] [Figure 1] Infrared spectrum of the composite oxide support in Example 1 of the present invention.

[0088] [Figure 2] TEM image of supported catalyst A in Example 13 of the present invention.

[0089] [Figure 3] Infrared spectrum of the untreated TiO2-SiO2 composite support in comparative test example 1.

[0090] [Figure 4] Infrared spectrum of the surface-treated SiO2 support in comparative test example 5.

[0091] [Figure 5] This is a comparison diagram of the infrared spectra of the carriers in Example 1, Comparative Test Example 1, and Comparative Test Example 5.

[0092] [Detailed description of the invention] To better understand the present invention, it will be described in detail below with reference to examples. These examples are for illustrative purposes only and do not limit the scope of application of the present invention.

[0093] In the following examples and comparative examples: (1) The SiO2 microsphere carrier was purchased from Shandong Bangkai Materials Co., Ltd.

[0094] (2) Dimethyl dioctadecylammonium chloride was purchased from J&K Scientific (CAS number: 61789-80-8).

[0095] (3) Cetyltrimethylammonium chloride was purchased from J&K Scientific (CAS number: 112-02-7).

[0096] (4) C chloride 12-14 Alkyldimethylethylbenzylammonium was purchased from J&K Scientific (CAS number: 85409-23-0).

[0097] (5) The Cu and its oxide content, in terms of CuO equivalent, was analyzed using an Optima 8300 ICP atomic emission spectrometer from Platinum Elmer (PE) (USA) in accordance with the JY / T 0567-2020 standard.

[0098] (6) The TiO2 content was measured using a spectrophotometer. The principle is as follows: Ti 4+ Titanium dioxide reacts with hydrogen peroxide to form a yellow complex. Titanium dioxide reacts with hot sulfuric acid to form titanyl sulfate, which reacts with hydrogen peroxide to form a stable orange-yellow complex [TiO(H2O2)]. 2- The following was formed. The measurement was performed at 430 nm using a Unico UV-2100 spectrophotometer.

[0099] (7) Similarly, the ZrO2 content was measured using a spectrophotometer.

[0100] (8) The infrared spectrum was measured using a Nicolet iS50 infrared spectrometer under the following conditions: sample preparation and scanning were performed in attenuated total reflection mode, with a scanning range of 4000–400 cm. -1 The resolution is 4cm. -1 The number of scans was 32.

[0101] (9) Conditions for TEM characterization: For HR-TEM characterization, the catalyst was observed using a Jem-3010 high-resolution transmission electron microscope at an accelerating voltage of 200 kV. Before the test, the sample was completely powdered, a small amount of the sample was added to anhydrous ethanol, and ultrasonically separated for 15-20 minutes in an ultrasonic cleaner (Model PS-10, Shenzhen Jiekang Ultrasonic Cleaner Co., Ltd.). Finally, the suspension was aspirated with a dropper, continuously dropped onto a microgrid, and then air-dried.

[0102] (10) The particle size of the copper atom clusters of the active ingredient was characterized by transmission electron microscopy (TEM) and measured based on a scale bar.

[0103] [Example 1] 85g of SiO2 microsphere carrier (particle size: 20μm, average pore size: 110nm, specific surface area: 78m²) 2 The material ( / g) was impregnated in 420 mL of a 0.45 mol / L titanium sulfate aqueous solution at 25°C for 6 hours. The resulting precipitate was dried at 110°C for 6 hours, and then roasted at 550°C for 5 hours to obtain a TiO2-SiO2 composite support with a TiO2 content of 15% by weight (and an SiO2 content of 85% by weight).

[0104] An impregnation solution was prepared by adding 95 g of o-xylene to 5 g of dimethyldioctadecylammonium chloride and uniformly mixing it with 10 mL of hydrochloric acid (mass fraction: 37 wt%). The TiO2-SiO2 composite support was impregnated with the impregnation solution at 20°C for 2 hours, and then dried at 60°C for 12 hours to obtain a TiO2-SiO2 composite oxide support.

[0105] The obtained composite oxide support was characterized by infrared spectroscopy. The infrared spectrum, i.e., the infrared spectrum of the surface-treated SiO2-TiO2 composite oxide, is shown in Figure 1. From the infrared spectrum, the surface properties of the composite oxide support of Example 1 are such that its infrared spectrum is 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1 It can be seen that it exhibits three characteristic peaks in the range of 620 cm⁻¹. Specifically, the infrared spectrum is 620 cm⁻¹. -1 , 649cm -1 , and 708cm -1 It shows a characteristic peak at 2850 cm. -1 , 2919cm -1 , and 2955cm -1 It also showed characteristic peaks.

[0106] [Example 2] The method for preparing the TiO2-SiO2 composite support was the same as in Example 1, except that 420 mL of a dilute sulfuric acid solution of metatitanic acid with a concentration of 0.86 mol / L was used instead of 420 mL of a 0.45 mol / L aqueous titanium sulfate solution to obtain a TiO2-SiO2 composite support with a TiO2 content of 25% by weight (and an SiO2 content of 75% by weight).

[0107] 4 g of dimethyldioctadecylammonium chloride was mixed with 96 g of o-xylene and homogeneously with 8 mL of hydrochloric acid (mass fraction: 37 wt%) to prepare an impregnation solution. The TiO2-SiO2 composite support was impregnated with the impregnation solution at 20°C for 2 hours, and then dried at 60°C for 12 hours to obtain a TiO2-SiO2 composite oxide support.

[0108] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support was similar to that of the composite oxide support in Example 1. The surface properties were such that its infrared spectrum was 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1 It showed three characteristic peaks within that range.

[0109] [Example 3] The method for preparing the TiO2-SiO2 composite support was the same as in Example 1, except that 398 mL of a 0.38 mol / L titanium tetrachloride aqueous solution was used instead of 420 mL of a 0.45 mol / L titanium sulfate aqueous solution to obtain a TiO2-SiO2 composite support with a TiO2 content of 12% by weight (and an SiO2 content of 88% by weight).

[0110] 3 g of dimethyldioctadecylammonium chloride was mixed with 97 g of o-xylene and homogeneously with 7 mL of hydrochloric acid (mass fraction: 37 wt%) to prepare an impregnation solution. The TiO2-SiO2 composite support was impregnated with the impregnation solution at 20°C for 2 hours, and then dried at 60°C for 12 hours to obtain a TiO2-SiO2 composite oxide support.

[0111] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support was similar to that of the composite oxide support in Example 1. The surface properties were such that its infrared spectrum was 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1 It showed three characteristic peaks within that range.

[0112] [Example 4] The method for preparing the TiO2-SiO2 composite support was the same as in Example 1, except that 360 mL of a 0.63 mol / L ethanol solution of tetrabutyl titanate was used instead of 420 mL of a 0.45 mol / L aqueous titanium sulfate solution to obtain a TiO2-SiO2 composite support with a TiO2 content of 18% by weight (and an SiO2 content of 82% by weight).

[0113] An impregnation solution was prepared by adding 98 g of o-xylene to 2 g of dimethyldioctadecylammonium chloride and uniformly mixing it with 5 mL of hydrochloric acid (mass fraction: 37 wt%). The TiO2-SiO2 composite support was impregnated with the impregnation solution at 20°C for 2 hours, and then dried at 60°C for 12 hours to obtain a TiO2-SiO2 composite oxide support.

[0114] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support was similar to that of the composite oxide support in Example 1. The surface properties were such that its infrared spectrum was 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1 It showed three characteristic peaks within that range.

[0115] [Example 5] The method for preparing the TiO2-SiO2 composite support was the same as in Example 1, except that 123 mL of a 0.51 mol / L ethanol solution of tetrabutyl titanate was used instead of 420 mL of a 0.45 mol / L aqueous titanium sulfate solution to obtain a TiO2-SiO2 composite support with a TiO2 content of 5% by weight (and an SiO2 content of 95% by weight).

[0116] An impregnation solution was prepared by adding 99 g of o-xylene to 1 g of cetyltrimethylammonium chloride and uniformly mixing it with 3 mL of hydrochloric acid (mass fraction: 37 wt%). The TiO2-SiO2 composite support was impregnated with the impregnation solution at 20°C for 4 hours, and then dried at 80°C for 12 hours to obtain a TiO2-SiO2 composite oxide support.

[0117] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support was similar to that of the composite oxide support in Example 1. The surface properties were such that its infrared spectrum was 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1 It showed three characteristic peaks within that range.

[0118] [Example 6] The method for preparing the TiO2-SiO2 composite support was the same as in Example 1, except that instead of roasting at 550°C for 5 hours, roasting was performed at 650°C for 7 hours to obtain a TiO2-SiO2 composite support with a TiO2 content of 15% by weight (and an SiO2 content of 85% by weight).

[0119] 5g of C chloride 12-14-An impregnation solution was prepared by adding 95 g of o-xylene to alkyldimethylethylbenzylammonium and uniformly mixing it with 10 mL of hydrochloric acid (mass fraction: 37 wt%). The TiO2-SiO2 composite support was impregnated with the impregnation solution at 40°C for 2 hours, and then dried at 100°C for 12 hours to obtain a TiO2-SiO2 composite oxide support.

[0120] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support was similar to that of the composite oxide support in Example 1. The surface properties were such that its infrared spectrum was 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1 It showed three characteristic peaks within that range.

[0121] [Example 7] The preparation method was the same as in Example 1, except that 420 mL of a 0.29 mol / L aqueous solution of zirconium tetrachloride was used instead of an aqueous titanium sulfate solution to obtain a ZrO2-SiO2 composite support with a ZrO2 content of 15% by weight (and an SiO2 content of 85% by weight).

[0122] An impregnation solution was prepared by adding 95 g of o-xylene to 5 g of dimethyldioctadecylammonium chloride and uniformly mixing it with 10 mL of hydrochloric acid (mass fraction: 37 wt%). The ZrO2-SiO2 composite support was impregnated with the impregnation solution at 20°C for 2 hours, and then dried at 60°C for 12 hours to obtain a ZrO2-SiO2 composite oxide support.

[0123] The infrared spectrum of the obtained ZrO2-SiO2 composite oxide support was similar to that of the composite oxide support in Example 1. The surface properties were such that its infrared spectrum was 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1 It showed three characteristic peaks within that range.

[0124] [Example 8] 85 g of SiO2 microsphere carriers were impregnated in 280 mL of 0.45 mol / L titanium sulfate aqueous solution at 25°C for 6 hours. The resulting precipitate was dried at 110°C for 6 hours and then roasted at 550°C for 5 hours. Furthermore, 300 mL of 0.14 mol / L zirconium nitrate aqueous solution was impregnated at 25°C for 4 hours, the resulting precipitate was dried at 110°C for 8 hours and then roasted at 550°C for 6 hours.

[0125] This resulted in a TiO2-ZrO2-SiO2 composite support having a TiO2 content of 10% by weight, a ZrO2 content of 5% by weight (and an SiO2 content of 85% by weight).

[0126] An impregnation solution was prepared by adding 95 g of o-xylene to 5 g of dimethyldioctadecylammonium chloride and uniformly mixing it with 10 mL of hydrochloric acid (mass fraction: 37 wt%). The TiO2-ZrO2-SiO2 composite support was impregnated with the impregnation solution at 20°C for 2 hours, and then dried at 60°C for 12 hours to obtain a TiO2-ZrO2-SiO2 composite oxide support.

[0127] The infrared spectrum of the obtained TiO2-ZrO2-SiO2 composite oxide support was similar to that of the composite oxide support in Example 1. The surface properties were such that its infrared spectrum was 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1 It showed three characteristic peaks within that range.

[0128] [Example 9] The method for preparing the TiO2-SiO2 composite oxide support involves replacing the SiO2 microsphere support of Example 1 with a particle size of 10 μm, an average pore size of 200 nm, and a specific surface area of ​​60 m². 2 The procedure was the same as in Example 1, except that a SiO2 microsphere carrier of / g was used.

[0129] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support was similar to that of the composite oxide support in Example 1. The surface properties were such that its infrared spectrum was 610-720 cm⁻¹. -1It shows three characteristic peaks in the range of 2840-2970 cm². -1 It showed three characteristic peaks within that range.

[0130] [Example 10] The method for preparing the TiO2-SiO2 composite oxide support involves using a particle size of 5 μm, an average pore size of 120 nm, and a specific surface area of ​​75 m² instead of the SiO2 microsphere support of Example 1. 2 The procedure was the same as in Example 1, except that a SiO2 microsphere carrier of / g was used.

[0131] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support was similar to that of the composite oxide support in Example 1. The surface properties were such that its infrared spectrum was 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1 It showed three characteristic peaks within that range.

[0132] [Example 11] The method for preparing the TiO2-SiO2 composite oxide support involves replacing the SiO2 microsphere support of Example 1 with a particle size of 30 μm, an average pore size of 1000 nm, and a specific surface area of ​​37 m². 2 The procedure was the same as in Example 1, except that a SiO2 microsphere carrier of / g was used.

[0133] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support was similar to that of the composite oxide support in Example 1. The surface properties were such that its infrared spectrum was 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1 It showed three characteristic peaks within that range.

[0134] [Example 12] The method for preparing the TiO2-SiO2 composite oxide support was the same as in Example 1, except that pyridine was used instead of o-xylene as the solvent in the impregnation solution.

[0135] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support was similar to that of the composite oxide support in Example 1. The surface properties were such that its infrared spectrum was 610-720 cm⁻¹. -1 It shows three characteristic peaks in the range of 2840-2970 cm². -1 It showed three characteristic peaks within that range.

[0136] [Example 13] To obtain Cu / TiO2-SiO2 catalysts (supported catalysts A-I, L, M, N, O) with a Cu / TiO2-SiO2 content of 5-25% by weight of Cu and its oxides, respectively, 100 g each was impregnated with 500 mL of an aqueous copper nitrate solution containing 5.26-33.33 g of Cu (in CuO equivalent) at 25°C for 180 minutes, dried at 110°C for 6 hours, and then roasted at 500°C for 4 hours. Details are shown in Table 1.

[0137] The prepared supported catalyst A was characterized by TEM, and the results are shown in Figure 2. From Figure 2, it can be seen that the active components were uniformly dispersed, the particle size of the atomic clusters of the active components was 2-5 nm, and the average particle size was 3.3 nm.

[0138] [Example 13] 100 g of the composite oxide support prepared in Example 1 was impregnated with 500 mL of an aqueous copper nitrate solution containing 32 g of Cu at 20°C for 180 minutes, then dried at 110°C for 6 hours, and subsequently roasted at 600°C for 6 hours to obtain a Cu / TiO2-SiO2 catalyst (supported catalyst J) with a Cu and oxide content of 24% by weight in terms of CuO. Details are shown in Table 1.

[0139] [Example 14] 100 g of the composite oxide support prepared in Example 1 was impregnated with 500 mL of an aqueous copper nitrate solution containing 32 g of Cu at 30°C for 180 minutes, then dried at 110°C for 6 hours, and subsequently roasted at 650°C for 7 hours to obtain a Cu / TiO2-SiO2 catalyst (supported catalyst K) with a Cu and oxide content of 24% by weight in terms of CuO. Details are shown in Table 1.

[0140] [Table 1]

[0141] The particle size, average pore size, and specific surface area of ​​supported catalysts A to N were measured, and the results are shown in Table 2. Here, the particle size was measured using a Malvern MS2000 laser particle size analyzer according to the test method specified in NB / SH / T 0951-2017.

[0142] The average pore size and specific surface area were measured using the mercury intrusion porosimetry method specified in GB / T 21650.1-2008 (Measurement of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption method - Part 1: Mercury intrusion porosimetry method) with an AutoPore IV 9500 high-performance fully automated mercury porosimemeter manufactured by Micromeristics Instrument Corporation (USA).

[0143] [Table 2]

[0144] [Test Example 1] To 2 L of a 4 wt% NBR chlorobenzene solution (prepared by dissolving NBR in chlorobenzene), 8 g of supported catalyst A, 0.4 g of homogeneous catalyst rhodium triphenylphosphine chloride, and 1.0 g of triphenylphosphine were added. The catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of 90°C, 6 MPa hydrogen pressure, and 8 hours to obtain a rubber solution, thereby obtaining HNBR.

[0145] The degree of hydrogenation of the obtained HNBR was measured according to the method specified in SH / T 1762-2008 / ISO 14558:2000 (Degree of unsaturation measurement). As a result, the degree of hydrogenation was 95.2%.

[0146] The selectivity of the obtained HNBR was measured by infrared spectroscopy using a Nicolet 560 FTIR spectrometer from Nicolet Instruments, Inc. (USA). The measurement results showed that the intensity of the -CN absorption peak in the infrared spectrum did not decrease after hydrogenation, and no absorption peak representing -NH2 appeared. This indicates that the -CN group remained unchanged before and after the reaction, and that -CN was not hydrogenated, resulting in 100% selectivity. The result demonstrated 100% selectivity.

[0147] [Test Example 2] To 2 L of a 4 wt% NBR chlorobenzene solution (prepared by dissolving NBR in chlorobenzene), 8 g of supported catalyst A, 0.4 g of homogeneous catalyst rhodium triphenylphosphine chloride, and 1.0 g of triphenylphosphine were added. The catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of 90°C, 8 MPa hydrogen pressure, and 6 hours to obtain a rubber solution, thereby obtaining HNBR.

[0148] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 96.1% and the selectivity was 100%.

[0149] [Test Example 3] To 2 L of a 4 wt% NBR chlorobenzene solution (prepared by dissolving NBR in chlorobenzene), 8 g of supported catalyst B, 0.4 g of homogeneous catalyst rhodium triphenylphosphine chloride, and 1.0 g of triphenylphosphine were added. The catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of a temperature of 90°C, a hydrogen pressure of 8 MPa, and a reaction time of 6 hours to obtain a rubber solution, thereby obtaining HNBR.

[0150] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 93.8% and the selectivity was 100%.

[0151] [Test Example 4] To 2 L of a chlorobenzene solution of 3 wt% NBR (prepared by dissolving NBR in chlorobenzene), 8 g of supported catalyst C, 0.5 g of homogeneous catalyst rhodium triphenylphosphine chloride, and 1.2 g of triphenylphosphine were added. The catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of a temperature of 90°C, a hydrogen pressure of 8 MPa, and a reaction time of 6 hours to obtain a rubber solution, thereby obtaining HNBR.

[0152] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 97.1% and the selectivity was 100%.

[0153] [Test Example 5] To 2 L of a chlorobenzene solution of 3 wt% NBR (prepared by dissolving NBR in chlorobenzene), 8 g of supported catalyst A, 0.4 g of homogeneous catalyst rhodium triphenylphosphine chloride, and 1.0 g of triphenylphosphine were added. The catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of a temperature of 90°C, a hydrogen pressure of 8 MPa, and a reaction time of 6 hours to obtain a rubber solution, thereby obtaining HNBR.

[0154] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 97.6% and the selectivity was 100%.

[0155] [Test Example 6] After the reaction in Test Example 5 was completed, supported catalyst A was recovered by centrifugation, washed with stirring in chlorobenzene (an organic solvent) for 4 hours, and then centrifuged. Using the same reaction conditions as in Test Example 5, the catalyst was re-added to the reaction system, and its catalytic performance for the hydrogenation of NBR was investigated. The experiment was conducted four times consecutively. The results for the degree of hydrogenation (measured according to the method in Test Example 1) and selectivity (determined by comparing the -CN group content in the raw materials and the hydrogenation product using nuclear magnetic resonance spectroscopy) are shown in Table 3.

[0156] [Table 3]

[0157] [Test Example 7] To 2 L of a 4 wt% NBR chlorobenzene solution (prepared by dissolving NBR in chlorobenzene), 8 g of supported catalyst D, 0.4 g of homogeneous catalyst rhodium triphenylphosphine chloride, and 1.0 g of triphenylphosphine were added. The catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of 90°C, 8 MPa hydrogen pressure, and 6 hours to obtain a rubber solution, thereby obtaining HNBR.

[0158] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 97.6% and the selectivity was 100%.

[0159] [Test Example 8] Except for using supported catalyst E instead of supported catalyst A, HNBR was ultimately obtained according to the method of Test Example 1.

[0160] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 91.2% and the selectivity was 100%.

[0161] [Test Example 9] Except for using supported catalyst F instead of supported catalyst A, HNBR was ultimately obtained according to the method of Test Example 1.

[0162] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 94.1% and the selectivity was 100%.

[0163] [Test Example 10] Except for using supported catalyst G instead of supported catalyst A, HNBR was ultimately obtained according to the method of Test Example 1.

[0164] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 95.1% and the selectivity was 100%.

[0165] [Test Example 11] Except for using supported catalyst H instead of supported catalyst A, HNBR was ultimately obtained according to the method of Test Example 1.

[0166] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 95.8% and the selectivity was 100%.

[0167] [Test Example 12] HNBR was finally obtained following the method of Test Example 1, except that supported catalyst I was used instead of supported catalyst A.

[0168] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 95.4% and the selectivity was 100%.

[0169] [Test Example 13] HNBR was finally obtained according to the method of Test Example 1, except that supported catalyst J was used instead of supported catalyst A.

[0170] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 95.7% and the selectivity was 100%.

[0171] [Test Example 14] Except for using supported catalyst K instead of supported catalyst A, HNBR was ultimately obtained according to the method of Test Example 1.

[0172] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 94.8% and the selectivity was 100%.

[0173] [Test Example 15] Except for using supported catalyst L instead of supported catalyst A, HNBR was ultimately obtained according to the method of Test Example 1.

[0174] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 95.3% and the selectivity was 100%.

[0175] [Test Example 16] Except for using supported catalyst M instead of supported catalyst A, HNBR was ultimately obtained according to the method of Test Example 1.

[0176] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 95.0% and the selectivity was 100%.

[0177] [Test Example 17] Except for using supported catalyst N instead of supported catalyst A, HNBR was ultimately obtained according to the method of Test Example 1.

[0178] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 96.1% and the selectivity was 100%.

[0179] [Test Example 18] HNBR was finally obtained according to the method of Test Example 1, except that the reaction conditions used were a temperature of 80°C, a hydrogen pressure of 6 MPa, and a reaction time of 8 hours.

[0180] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 93.9% and the selectivity was 100%.

[0181] [Test Example 19] HNBR was finally obtained according to the method of Test Example 1, except that the reaction conditions used were a temperature of 70°C, a hydrogen pressure of 6 MPa, and a reaction time of 8 hours.

[0182] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 91.7% and the selectivity was 100%.

[0183] [Test Example 20] HNBR was finally obtained according to the method of Test Example 1, except that the reaction conditions used were a temperature of 60°C, a hydrogen pressure of 6 MPa, and a reaction time of 8 hours.

[0184] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 90.2% and the selectivity was 100%.

[0185] [Test Example 21] HNBR was finally obtained according to the method of Test Example 1, except that the reaction conditions used were a temperature of 50°C, a hydrogen pressure of 6 MPa, and a reaction time of 8 hours.

[0186] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 88.2% and the selectivity was 100%.

[0187] [Test Example 22] To 2 L of a 4 wt% NBR chlorobenzene solution (prepared by dissolving NBR in chlorobenzene), 8 g of supported catalyst A, 0.4 g of homogeneous catalyst rhodium triphenylphosphine chloride, and 1.2 g of triphenylphosphine were added. The catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of a temperature of 90°C, a hydrogen pressure of 6 MPa, and a reaction time of 8 hours to obtain a rubber solution, thereby obtaining HNBR.

[0188] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 95.3% and the selectivity was 100%.

[0189] [Test Example 23] To 2 L of a 4 wt% NBR chlorobenzene solution (prepared by dissolving NBR in chlorobenzene), 8 g of supported catalyst A, 0.4 g of homogeneous catalyst rhodium triphenylphosphine chloride, and 1.6 g of triphenylphosphine were added. The catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of 90°C, 6 MPa hydrogen pressure, and 8 hours to obtain a rubber solution, thereby obtaining HNBR.

[0190] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 95.4% and the selectivity was 100%.

[0191] [Test Example 24] To 2 L of a 4 wt% NBR chlorobenzene solution (prepared by dissolving NBR in chlorobenzene), 8 g of supported catalyst A, 0.4 g of homogeneous catalyst rhodium triphenylphosphine chloride, and 2 g of triphenylphosphine were added. The catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of a temperature of 90°C, a hydrogen pressure of 6 MPa, and a reaction time of 8 hours to obtain a rubber solution, thereby obtaining HNBR.

[0192] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 95.3% and the selectivity was 100%.

[0193] [Test Example 25] To 2 L of a 4 wt% NBR chlorobenzene solution (prepared by dissolving NBR in chlorobenzene), 12 g of supported catalyst A, 0.4 g of homogeneous catalyst rhodium triphenylphosphine chloride, and 1.6 g of triphenylphosphine were added. The catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of a temperature of 90°C, a hydrogen pressure of 6 MPa, and a reaction time of 8 hours to obtain a rubber solution, thereby obtaining HNBR.

[0194] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 98.9% and the selectivity was 100%.

[0195] [Test Example 26] To 2 L of a 4 wt% NBR chlorobenzene solution (prepared by dissolving NBR in chlorobenzene), 8 g of supported catalyst A, 0.08 g of homogeneous catalyst rhodium triphenylphosphine chloride, and 0.32 g of triphenylphosphine were added. The catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of a temperature of 95°C, a hydrogen pressure of 8 MPa, and a reaction time of 8 hours to obtain a rubber solution, thereby obtaining HNBR.

[0196] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 91.3% and the selectivity was 100%.

[0197] [Test Example 27] To 2 L of a 4 wt% NBR chlorobenzene solution (prepared by dissolving NBR in chlorobenzene), 8 g of supported catalyst A, 0.7 g of homogeneous catalyst ruthenium triphenylphosphine chloride, and 1.5 g of triphenylphosphine were added. The catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of 90°C, 6 MPa hydrogen pressure, and 8 hours to obtain a rubber solution, thereby obtaining HNBR.

[0198] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 95.2% and the selectivity was 100%.

[0199] [Test Example 28] HNBR was finally obtained according to the method of Test Example 1, except that supported catalyst O was used instead of supported catalyst A.

[0200] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 95.7% and the selectivity was 100%.

[0201] [Comparative Test Example 1] The infrared spectrum of the non-surface-treated TiO2-SiO2 composite oxide support used in Example 1 is shown in Figure 3.

[0202] Subsequently, the active ingredient was supported according to the method of Example 12, and a Cu / TiO2-SiO2 catalyst with a Cu content of 24 wt% was finally obtained. The particle size of the Cu atomic clusters was 20-50 nm.

[0203] Following the method of Test Example 1, HNBR was finally obtained.

[0204] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 88.2% and the selectivity was 99%.

[0205] [Comparative Test Example 2] Using the TiO2-SiO2 composite oxide support from Example 1, and except that nickel nitrate solution was used instead of copper nitrate solution, a Ni / ZrO2-SiO2 catalyst (supported catalyst DB1) with a final Ni content of 24 wt% was obtained according to the method of Example 5. The particle size of the Ni atomic clusters was 10-30 nm.

[0206] HNBR was ultimately obtained following the method of Test Example 1, except that supported catalyst DB1 was used instead of supported catalyst A.

[0207] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 78% and the selectivity was 82.5%.

[0208] [Comparative Test Example 3] The procedure followed that of Test Example 1, except that only supported catalyst A was used. The specific steps were as follows: To 2 L of a chlorobenzene solution of 3 wt% NBR (prepared by dissolving NBR in chlorobenzene), 9.4 g of supported catalyst A was added, and a catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of 90°C, 8 MPa hydrogen pressure, and 6 hours to obtain a rubber solution, thereby obtaining HNBR.

[0209] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 57.6% and the selectivity was 100%.

[0210] [Comparative Test Example 4] The procedure followed the method of Test Example 5, except that only a homogeneous catalyst was used. The specific steps were as follows: To 2 L of a chlorobenzene solution of 3 wt% NBR (prepared by dissolving NBR in chlorobenzene), 0.4 g of rhodium triphenylphosphine chloride and 1.0 g of triphenylphosphine, which are homogeneous catalysts, were added, and a catalytic hydrogenation reaction was carried out in an autoclave under reaction conditions of 90°C, 8 MPa hydrogen pressure, and 6 hours to obtain a rubber solution, thereby obtaining HNBR.

[0211] The degree of hydrogenation and selectivity of the obtained HNBR were measured according to the method of Test Example 1. As a result, the degree of hydrogenation was 67.2% and the selectivity was 100%.

[0212] [Comparative Test Example 5] 85 g of SiO2 microsphere carrier (particle size: 20 μm, average pore size: 110 nm) was extracted.

[0213] An impregnation solution was prepared by adding 95 g of o-xylene to 5 g of dimethyldioctadecylammonium chloride and uniformly mixing it with 10 mL of hydrochloric acid (mass fraction: 37 wt%). The SiO2 microsphere carrier was immersed in the impregnation solution at 20°C for 2 hours, and then dried at 60°C for 12 hours.

[0214] Figure 4 shows the infrared spectrum of the surface-treated SiO2 support.

[0215] From FIGS. 1 and 3 to 5, after the composite oxide carrier is surface-treated with an impregnation solution containing an organic cationic quaternary ammonium salt, the surface characteristics of the obtained surface-treated composite oxide carrier are such that its infrared spectrum shows three characteristic peaks in the range of 610 to 720 cm -1 and shows three characteristic peaks in the range of 2840 to 2970 cm -1 . In contrast, neither the infrared spectrum of the non-surface-treated TiO2-SiO2 composite oxide carrier nor the infrared spectrum of the surface-treated SiO2 carrier shows three characteristic peaks in the range of 610 to 720 cm -1 , nor do they show three characteristic peaks in the range of 2840 to 2970 cm -1 . The composite oxide carrier of the present invention can greatly improve the dispersibility of the active component on the catalyst surface and control the atomic cluster size of the active component to 5 nm or less, thus significantly improving the hydrogenation activity of the catalyst.

[0216] From Test Examples 1 to 27 and Comparative Test Examples 1 to 4, by adopting a synergistic cooperation method with a homogeneous catalyst, the present invention ensures the hydrogenation saturation of the polymer material at relatively low temperatures and pressures, achieves a high degree of hydrogenation of the obtained HNBR product, and furthermore, it can be ensured that the supported catalyst can be reused multiple times, and it can be seen that the separation and recovery of the catalyst are easy.

[0217] The above are only preferred embodiments of the present invention. Those skilled in the art can also make other equivalent changes and improvements under the technical concept provided by the present invention as common knowledge in the field, and these should also be regarded as within the protection scope of the present invention.

Brief Description of the Drawings

[0218] [Figure 1] It is the infrared spectrum of the composite oxide carrier in Example 1 of the present invention. [Figure 2] It is the TEM image of the supported catalyst A in Example 13 of the present invention. [Figure 3] It is the infrared spectrum of the non-surface-treated TiO2-SiO2 composite carrier in Comparative Test Example 1. [Figure 4] This is the infrared spectrum of the surface-treated SiO2 support in comparative test example 5. [Figure 5] This is a comparison diagram of the infrared spectra of the carriers in Example 1, Comparative Test Example 1, and Comparative Test Example 5.

Claims

1. SiO ２ and a composite oxide support comprising a group IVB metal oxide, wherein the group IVB metal oxide is TiO ２ and / or ZrO ２ The composite oxide support has an infrared spectrum of 610-720 cm⁻¹. －１ It shows three characteristic peaks in the range of 2840–2970 cm². －１ A composite oxide support characterized by having surface properties that exhibit three characteristic peaks within a certain range.

2. The composite oxide carrier has a surface property such that its infrared spectrum shows characteristic peaks at 620 ± 1 cm －１ , 649 ± 1 cm －１ , and 708 ± 1 cm －１ ; and / or the composite oxide carrier has a surface property such that its infrared spectrum shows characteristic peaks at 2850 ± 1 cm －１ , 2919 ± 1 cm －１ , and 2955 ± 1 cm －１ . The composite oxide carrier according to claim 1, characterized by this.

3. The composite oxide support is SiO ２ The composite oxide support precursor, which includes a group IVB metal oxide, is obtained by subjecting it to a surface treatment using an impregnation solution containing an organic cationic quaternary ammonium salt, preferably the surface treatment being impregnation and drying; preferably the organic cationic quaternary ammonium salt is C ６ + Long-chain alkyl quaternary ammonium salt, preferably halogenated C ６ + Long-chain alkyl quaternary ammonium salts, more preferably dimethyldioctadecylammonium chloride, cetyltrimethylammonium chloride, and C chloride １２－１４ - The composite oxide support according to claim 1, characterized in that it is at least one selected from alkyldimethylethylbenzylammonium.

4. Based on the total weight of the composite oxide support, the content of the IVB group metal oxide is 5 to 25% by weight, and the SiO ２ The content of is 75 to 95% by weight, preferably the content of the IVB group metal oxide is 10 to 25% by weight, and the SiO ２ The content is 75 to 90% by weight; and / or the particle size of the composite oxide support is 5 to 30 μm; and / or the average pore size is 100 to 1200 nm; and / or the specific surface area is 30 to 200 m². ２ The composite oxide support according to any one of claims 1 to 3, characterized in that it is / g.

5. A method for preparing a composite oxide support according to any one of claims 1 to 4, characterized by including the following steps: (1) SiO ２ A step of obtaining a composite oxide carrier precursor by subjecting a microsphere carrier to a first impregnation using a solution of a group IVB metal compound, followed by a first drying and a first roasting, wherein the group IVB metal compound is a titanium-containing compound and / or a zirconium-containing compound; (2) A step of obtaining a composite oxide support by subjecting the composite oxide support precursor to a surface treatment using an impregnation solution containing an organic cationic quaternary ammonium salt.

6. The impregnation solution containing the organic cationic quaternary ammonium salt comprises the organic cationic quaternary ammonium salt, a solvent, and an acid; Preferably, the method according to 5, wherein the concentration of the quaternary ammonium salt in the impregnation solution containing the organic cationic quaternary ammonium salt is 0.1 to 10% by weight.

7. The aforementioned organic cationic quaternary ammonium salt is C ６ + Long-chain alkyl quaternary ammonium salt, preferably halogenated C ６ + Long-chain alkyl quaternary ammonium salts, more preferably dimethyldioctadecylammonium chloride, cetyltrimethylammonium chloride, and C chloride １２－１４ - At least one selected from alkyldimethylethylbenzylammonium; and / or The solvent is at least one selected from deionized water, methanol, ethanol, acetone, methyl ethyl ketone, tetrahydrofuran, o-xylene, p-xylene, and pyridine, preferably at least one selected from o-xylene, p-xylene, and pyridine, more preferably o-xylene or pyridine; and / or The acid is at least one selected from hydrochloric acid, sulfuric acid, nitric acid, and citric acid, preferably hydrochloric acid. The method according to feature 6.

8. The method according to any one of claims 5 to 7, wherein the surface treatment comprises impregnation and drying, preferably the impregnation conditions being a temperature of 20 to 60°C and a time of 0.5 to 8 hours; and the drying conditions being a temperature of 50 to 120°C and a time of 2 to 10 hours.

9. The SiO ２ The particle size of the microsphere carrier 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 The method according to any one of claims 5 to 8, characterized in that it is / g.

10. The titanium-containing compound is at least one selected from titanium sulfate, metatitanic acid, titanium tetrachloride, and tetrabutyl titanate; and / or, The zirconium-containing compound is at least one selected from zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconyl chloride, and zirconium oxalate; and / or, The method according to any one of claims 5 to 9, characterized in that the concentration of the titanium-containing compound and / or zirconium-containing compound in the solution of the titanium-containing compound and / or zirconium-containing compound is 0.1 to 1.0 mol / L.

11. The SiO ２ The method according to any one of claims 5 to 10, characterized in that the molar ratio of the microsphere carrier to the IVB metal-containing compound is 3 to 40:1; and / or the first impregnation conditions are a temperature of 20 to 60°C and a time of 0.5 to 8 hours; and / or the first drying conditions are a temperature of 105 to 130°C and a time of 2 to 8 hours; and / or the first roasting conditions are a temperature of 450 to 650°C and a time of 3 to 8 hours.

12. A supported catalyst comprising a composite oxide support according to any one of claims 1 to 4, and Cu and its oxides as active components supported on the support, wherein the particle size of the copper atom clusters of the active component is 5 nm or less; and the content of Cu and its oxides in terms of CuO is 5 to 25% by weight, based on the total weight of the supported catalyst.

13. The particle size of the supported catalyst is 5 to 30 μm; and / or the average pore size is 100 to 1200 nm; and / or the specific surface area is 30 to 200 m². ２ The supported catalyst according to claim 12, characterized in that the amount is / g; and / or the particle size of the copper atom clusters of the active ingredient is 2 to 5 nm.

14. A method for preparing the supported catalyst according to claim 12 or 13, comprising the following steps: subjecting the composite oxide support according to any one of claims 1 to 4, or the composite oxide support obtained by the method according to any one of claims 5 to 9, to a second impregnation with a solution of soluble copper salt, followed by a second drying and a second roasting.

15. The method according to 14, characterized in that the molar ratio of the composite oxide support to the soluble copper salt is 1:0.03 to 0.6; and / or the second impregnation conditions are a temperature of 20 to 60°C and a time of 0.5 to 8 hours; and / or the second drying conditions are a temperature of 105 to 180°C and a time of 2 to 8 hours; and / or the second roasting conditions are a temperature of 450 to 650°C and a time of 3 to 8 hours.

16. The method according to 14 or 15, characterized in that the soluble copper salt is at least one selected from copper chloride, copper sulfate, copper nitrate, copper acetate, and disodium copper ethylenediaminetetraacetate.

17. A catalyst composition comprising a homogeneous catalyst and the supported catalyst described in claim 12 or 13.

18. The homogeneous catalyst comprises triphenylphosphine and triphenylphosphine chloride of a platinum group metal; Preferably, the platinum group metal triphenylphosphine chloride is rhodium triphenylphosphine chloride and / or ruthenium triphenylphosphine chloride; Preferably, the weight ratio of the triphenylphosphine to the platinum group metal to the triphenylphosphine chloride is 2 to 5:1, characterized in that the catalyst composition is as described in 17.

19. The catalyst composition according to claim 17 or 18, characterized in that the weight ratio of the supported catalyst to the homogeneous catalyst is 1:0.01 to 0.

3.

20. A method for hydrogenating a polymer, comprising dissolving the polymer in an organic solvent, then adding a catalyst composition according to any one of claims 17 to 19, and reacting the polymer with hydrogen in the presence of the catalyst composition.

21. The hydrogenation method according to claim 20, characterized in that the amount of the supported catalyst accounts for 5 to 20% by weight of the polymer.

22. The hydrogenation method according to claim 20, characterized in that the conditions for the reaction are a temperature of 30 to 90°C, a hydrogen pressure of 5 to 10 MPa, and a time of 5 to 10 hours.

23. The hydrogenation method according to any one of claims 20 to 22, characterized in that the polymer is NBR.

24. The hydrogenation method according to any one of claims 20 to 23, characterized in that the organic solvent is at least one selected from chlorobenzene, acetone, methyl ethyl ketone, tetrahydrofuran, dichloromethane, chloroform, cyclohexanone, ethyl acetate, and dimethylformamide.

25. A hydrogenated polymer obtained by the hydrogenation method described in any one of claims 20 to 24, preferably HNBR.

26. Use of a composite oxide carrier according to any one of claims 1 to 4, a composite oxide carrier obtained by the method according to any one of claims 5 to 11, a supported catalyst according to claim 12 or 13, a supported catalyst obtained by the method according to any one of claims 14 to 16, a catalyst composition according to any one of claims 17 to 19, a hydrogenated polymer obtained by the hydrogenation method according to any one of claims 20 to 24, or a hydrogenated polymer according to claim 25, in the manufacture of rubber products or the same, particularly in the manufacture of HNBR products or the same.

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