COMPOSITE OXIDE CARRIER, CARRIER CATALYST AND HYDROGENATED NITRILE BUTADIENE RUBBER, AS WELL AS METHOD FOR THEIR MANUFACTURE AND THEIR USE

Abstract

The present invention discloses a composite oxide support, a supported catalyst, and hydrogenated nitrile butadiene rubber, as well as a process for their preparation and their use. The composite oxide support comprises SiO2 and a metal oxide of group IVB, wherein the metal oxide of group IVB is TiO2 and / or ZrO2, and the composite oxide support has such surface properties that three characteristic peaks in the infrared spectrum in the range of 610-720 cm⁻¹ are observed. -1 and three further characteristic peaks in the infrared spectrum in the range of 2840-2970 cm -1The composite oxide support of the present invention can significantly improve the dispersion of the active components on the surface of a catalyst and substantially enhance the hydrogenation activity of the catalyst. The supported catalyst of the present invention is used in combination with a homogeneous catalyst for the hydrogenation saturation of a high-molecular-weight polymer material at low temperature and low pressure, and the resulting high-molecular-weight polymer product (in particular, hydrogenated nitrile butadiene rubber) exhibits a high degree of hydrogenation. Furthermore, the supported catalyst of the present invention can be reused multiple times, thereby improving the recyclability of the catalyst and reducing manufacturing costs.

Description

Technical field

[0001] The present invention relates to a composite oxide support and a method for its production, a supported catalyst and a method for its production, as well as hydrogenated nitrile butadiene rubber and a method for its production and their use. State of the art

[0002] Nitrile butadiene rubber (NBR) is a copolymer polymerized from acrylonitrile and butadiene monomers, exhibiting excellent oil resistance, high wear resistance, good heat resistance, and strong adhesion. Its disadvantages include poor cold resistance, poor odor resistance, low insulating properties, and low elasticity. NBR is widely used in the manufacture of various oil-resistant rubber products in sectors such as automotive, aerospace, and petroleum.

[0003] Hydrogenated nitrile butadiene rubber (HNBR) is a product obtained through the catalytic selective hydrogenation of unsaturated olefin segments in the hydrocarbon chain of nitrile butadiene rubber (NBR). HNBR has excellent properties such as good oil resistance, heat resistance, chemical corrosion resistance, odor resistance, high tensile strength, and wear resistance.

[0004] Currently, the main method for the industrial production of HNBR is solution hydrogenation, which primarily includes homogeneous and heterogeneous hydrogenation. Homogeneous hydrogenation refers to the catalytic hydrogenation of a polymer under specific reaction conditions, where the active component of the catalyst is dispersed as molecules in the polymer solution. In homogeneous hydrogenation, the reactant and catalyst are mixed uniformly, the reaction conditions are easy to control, and the resulting product exhibits stable performance. However, a common disadvantage of the homogeneous solution hydrogenation process is the difficulty in separating the catalyst from the product.Although numerous technologies have been developed to address this problem, such as the use of ion-exchange resins for the ion exchange of precious metals, the utilization of tin chloride complexation with a rhodium catalyst for aqueous phase extraction and recovery of the precious metal rhodium, and the use of temperature-controlled phase-transfer catalysts, these methods make it difficult to completely remove the precious metal catalyst remaining in the polymer. Furthermore, gel formation can occur, impairing product quality, and the costs for large-scale implementation are extremely high. On the one hand, the residues of precious metals in hydrogenation products increase production costs and waste precious metal resources. On the other hand, they lead to accelerated aging of HNBR and impair the polymer's mechanical processability.

[0005] In contrast to homogeneous hydrogenation catalyst systems, heterogeneous catalytic reaction systems utilize noble metal supported catalysts, effectively solving the problem of separating the catalyst from the hydrogenated products. This not only enables the recycling of noble metal catalysts but also effectively prevents noble metal residues in the polymer. Currently, the production of supported catalysts is still based on the traditional impregnation process, which results in a large particle size of the active component and a significant reduction in the number of active sites. Furthermore, due to the weak interaction between the active component and the support, detachment and loss of noble metals from the support surface can easily occur after vigorous stirring, reducing catalyst availability and impairing the performance of the hydrogenation product.Zeon Corporation uses SiO2 as a support to load Pd metal for the hydrogenation of NBR, achieving a one-pass hydrogenation degree of over 95%. However, the catalyst exhibits poor performance upon repeated use; for example, activity begins to decrease on the second use, and by the third or fourth use, activity and hydrogenation levels drop significantly.

[0006] The homogeneous catalytic hydrogenation process achieves a high degree of hydrogenation; however, catalyst separation is difficult, and costs increase. The heterogeneous catalytic hydrogenation process for polymer saturation leads to an insufficiently high degree of hydrogenation. Furthermore, active components are lost during stirring in the reactor, or the catalyst's effectiveness is poor upon repeated use, resulting in a significant decrease in the degree of hydrogenation. Therefore, there is a need to develop a catalyst and corresponding utilization methods that not only ensure a high degree of hydrogenation and easy catalyst separation / recovery but also guarantee the repeated use of the heterogeneous catalyst.

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

[0008] With regard to the aforementioned problems of the prior art, the present invention offers a novel composite oxide support. The composite oxide support exhibits surface properties characterized by three characteristic peaks in its infrared (IR) spectrum in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1The support can significantly improve the dispersion of the active component on the catalyst surface and limit the size of the atomic clusters of the active component to a maximum of 5 nm, thereby significantly 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 components and exhibits small particle sizes. By employing a process of synergistic interaction with homogeneous catalysts, the present invention ensures the hydrogenation saturation of polymer materials at relatively low temperatures and pressures, and the resulting hydrogenated polymer products (e.g., HNBR) achieve a high degree of hydrogenation.Furthermore, the supported catalyst of the present invention can be reused multiple times, and the catalyst composition can be easily separated and recovered. In particular, the use of non-precious metals as active components for the production of the supported catalyst avoids the problem of loss of the active precious metal component, further improves the recoverability of the catalyst, and significantly reduces the cost of the catalyst, thereby lowering the production costs of hydrogenated polymers (e.g., HNBR).

[0009] A first aspect of the present invention is to provide a composite oxide support characterized in that it comprises SiO2 and a metal oxide of group IVB, wherein the metal oxide of group IVB is TiO2 and / or ZrO2. The composite oxide support has such surface properties that its infrared spectrum (IR spectrum) exhibits three characteristic peaks in the range of 610-720 cm⁻¹.-1 and three characteristic peaks in the range of 2840-2970 cm -1 The present invention features the following measurement conditions for the IR spectrum: A Nicolet iS50 IR spectrometer is used; sample preparation and scanning are performed in attenuated total reflection mode; the scan range is 4000-400 cm⁻¹. -1 The resolution is 4 cm. -1 and the number of scans is 32. As in Fig. As shown, the composite oxide support according to the present invention has, for example, such surface properties that its IR spectrum exhibits three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibits.

[0010] In some embodiments of the composite oxide support according to the present invention, the composite oxide support has such surface properties that its IR spectrum exhibits three characteristic peaks in the range of 620-710 cm⁻¹. -1 and three characteristic peaks in the range of 2850-2960 cm -1 exhibits.

[0011] In some embodiments of the composite oxide support according to the present invention, the composite oxide support has such surface properties that its IR spectrum exhibits characteristic peaks at 620 ± 1 cm⁻¹. -1 , 649 ± 1 cm -1 and 708 ± 1 cm -1 exhibits; and / or the composite oxide support has such surface properties that its IR spectrum shows characteristic peaks at 2850 ± 1 cm -1 , 2919 ± 1 cm -1 and 2955 ± 1 cm -1 exhibits.

[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 comprising SiO2 and a metal oxide of group IVB 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 C6 and longer (C6+) long-chain alkylquaternary ammonium salt, preferably a C6+ long-chain alkylquaternary ammonium halide salt. Preferably, the halogen is Cl, Br, or I, with Cl being more preferred. More preferably, the C6+ long-chain alkyl group is a C6-C 24 Alkyl group, preferably a C8-C 22 Alkyl group, even more preferably a C 10 -C 20 Alkyl group and even more preferably a C 12 -C18 Alkyl group. More preferably, the organic cationic quaternary ammonium salt of at least one selected from dimethyldioctadecylammonium chloride, cetyltrimethylammonium chloride and C 12-14 -Alkyldimethylethylbenzyl ammonium chloride.

[0014] In some embodiments of the composite oxide support according to the present invention, the surface treatment consists of impregnation and drying. That is, the entire surface treatment process of the composite oxide support precursor with the organic cationic quaternary ammonium salt does not include any treatment steps at high temperatures (e.g., temperatures above 300 °C) such as roasting, calcining, or sintering. In the IR spectrum of the composite oxide support according to the present invention, the three characteristic peaks are in the range of 610–720 cm⁻¹. -1 e.g. the three characteristic peaks in the range of 620-710 cm -1 or the characteristic peaks at 620 ± 1 cm -1, 649 ± 1 cm -1 , 708 ± 1 cm -1 , mainly due to C-halogen vibrations (e.g. C-Cl); the three characteristic peaks in the range of 2840-2970 cm⁻¹ -1 e.g. the three characteristic peaks in the range of 2850-2960 cm -1 or the characteristic peaks at 2850 ± 1 cm -1 , 2919 ± 1 cm -1 , 2955 ± 1 cm -1 , are mainly due to CH vibrations.

[0015] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the content of group IVB metal oxides, based on the total weight of the composite oxide support, is 5-25 wt.% and the content of SiO2 is 75-95 wt.%. For example, but not limited to, the content of group IVB metal oxides is 5-20 wt.%, 5-15 wt.%, 5-10 wt.%, 10-25 wt.%, 10-20 wt.%, 10-15 wt.%, 12-25 wt.%, 12-20 wt.%, 12-15 wt.%, 15-25 wt.%, 15-20 wt.%, 20-25 wt.% and the like; Accordingly, the SiO₂ content is 80-95 wt.%, 85-95 wt.%, 90-95 wt.%, 75-90 wt.%, 80-90 wt.%, 85-90 wt.%, 75-88 wt.%, 80-88 wt.%, 85-88 wt.%, 75-85 wt.%, 80-85 wt.%, 75-80 wt.%, and the like. Preferably, the content of metal oxide of group IVB is 10-25 wt.% and the content of SiO₂ is 75-90 wt.%. Preferably, the content of metal oxide of group IVB is more than 10-25 wt.%.-% and the SiO2 content is 75 to less than 90 wt.%. Preferably, the metal oxide content of group IVB is 11-25 wt.% and the SiO2 content is 75-89 wt.%. Preferably, the metal oxide content of group IVB is 12-25 wt.% and the SiO2 content is 75-88 wt.%. Preferably, the metal oxide content of group IVB is 15-25 wt.% and the SiO2 content is 75-85 wt.%.

[0016] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, in which the group IVB metal oxide is TiO2 and ZrO2, the ratio of TiO2 to ZrO2 can vary within a wide range. For example, but not limited to, the weight ratio of TiO2 to ZrO2 is 0.01-100:1, 0.05-20:1, 0.1-10:1, 0.3-3:1, 0.5-2:1, 1-100:1, 1-20:1, 1-10:1, 1-3:1, 1-2:1, 0.01-1:1, 0.05-1:1, 0.1-1:1, 0.3-1:1, 0.5-1:1.

[0017] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the composite oxide support has a particle size of 5-30 µm. For example, but not limited to, 5-25 µm, 5-20 µm, 5-15 µm, 5-10 µm, 10-30 µm, 10-25 µm, 10-20 µm, 10-15 µm, 15-30 µm, 15-25 µm, 15-20 µm, 20-30 µm, 20-25 µm and the like, including the range between any two of the above-mentioned values. In the present invention, the particle size of the composite oxide support is measured according to the test method specified in NB / SH / T 0951-2017 using the MS2000 laser particle size analyzer from Malvern.

[0018] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the composite oxide support has an average pore diameter of 100-1200 nm. For example, but not limited to, 100-1000 nm, 100-800 nm, 100-600 nm, 100-500 nm, 100-400 nm, 100-300 nm, 100-200 nm, 200-1200 nm, 200-1000 nm, 200-800 nm, 200-600 nm, 200-500 nm, 200-400 nm, 200-300 nm, 300-1200 nm, 300-1000 nm, 300-800 nm, 300-600 nm, 300-500 nm, 300-400 nm, 400-1200 nm, 400-1000 nm, 400-800 nm, 400-600 nm, 400-500 nm, 500-1200 nm, 500-1000 nm, 500-800 nm, 500-600 nm, 600-1200 nm, 600-1000 nm, 600-800 nm, 600-700 nm, 700-1200 nm, 700-1000 nm, 700-800 nm, 800-1200 nm, 800-1000 nm, 900-1200 nm, 900-1000 nm, 1000-1200 nm and the like, including the range between any two of the above The values ​​mentioned. In the present invention, the average pore diameter of the composite oxide support is determined according to GB / T 21650.1-2008 (Determination of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption methods - Part 1: Mercury intrusion porosimetry method) measured using a fully automated high-performance mercury porosimeter AutoPore IV 9500 from Micromeritics Instrument Corporation, USA.

[0019] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the composite oxide support has a specific surface area of ​​30-200 m². 2 / g. For example, but not limited to, 30-150 m 2 / g, 30-120 m 2 / g, 30-100 m 2 / g, 30-90 m 2 / g, 30-80 m 2 / g, 30-70 m 2 / g, 30-60 m 2 / 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 / g and the like, including the range between any two of the above-mentioned values. In the present invention, the specific surface area of ​​the composite oxide support is measured according to GB / T 21650.1-2008 (Determination of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption methods - Part 1: Mercury intrusion porosimetry method) using a fully automated high-performance mercury porosimeter AutoPore IV 9500 from Micromeritics Instrument Corporation, USA.

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

[0021] In some embodiments of the manufacturing process of the 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 fabrication process of the composite oxide support according to the present invention, the organic cationic quaternary ammonium salt is a C6+ long-chain alkylquaternary ammonium salt, preferably a C6+ long-chain alkylquaternary ammonium halide salt. Preferably, the halogen is Cl, Br, or I, with Cl being more preferred. Preferably, the C6+ long-chain alkyl group is a C6-C 24 Alkyl group, preferably a C8-C 22 Alkyl group, even more preferably a C 10 -C 20 Alkyl group and even more preferably a C 12 -C 18Alkyl group. More preferably, the organic cationic quaternary ammonium salt of at least one selected from dimethyldioctadecylammonium chloride, cetyltrimethylammonium chloride and C 12-14 -Alkyldimethylethylbenzyl ammonium chloride.

[0023] In some embodiments of the manufacturing process of the 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 manufacturing process for the composite oxide support according to the present invention, the acid is 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 1–98.3 wt.%.

[0025] In some embodiments of the manufacturing process of the 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 0.1–10 wt.%. More preferably, the weight ratio of the organic cationic quaternary ammonium salt to the solvent to the acid is 1:10–19:1–3. For example, the weight of 1 ml of 37 wt.% concentrated hydrochloric acid in the example is 1.18 g.

[0026] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the surface treatment consists of impregnation and drying. Preferably, the impregnation conditions include a temperature of 20–60 °C and a time of 0.5–8 h; the drying conditions include a temperature of 50–120 °C and a time of 2–10 h. The entire surface treatment process of the composite oxide support precursor with the organic cationic quaternary ammonium salt does not include any high-temperature treatment steps (e.g., at temperatures above 300 °C) such as roasting, calcining, or sintering. Thus, the groups of the organic cationic quaternary ammonium salt and the 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 components, thereby promoting their dispersion.

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

[0028] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the SiO2 microsphere support has a particle size of 5-30 µm. For example, but not limited to, 5-25 µm, 5-20 µm, 5-15 µm, 5-10 µm, 10-30 µm, 10-25 µm, 10-20 µm, 10-15 µm, 15-30 µm, 15-25 µm, 15-20 µm, 20-30 µm, 20-25 µm and the like, including the range between any two of the above values. In the present invention, the particle size of the SiO2 microsphere carrier is measured according to the test method specified in NB / SH / T 0951-2017 using the MS2000 laser particle size analyzer from Malvern.

[0029] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the SiO2 microsphere support has an average pore diameter of 100-1200 nm. For example, but not limited to, 100-1000 nm, 100-800 nm, 100-600 nm, 100-500 nm, 100-400 nm, 100-300 nm, 100-200 nm, 200-1200 nm, 200-1000 nm, 200-800 nm, 200-600 nm, 200-500 nm, 200-400 nm, 200-300 nm, 300-1200 nm, 300-1000 nm, 300-800 nm, 300-600 nm, 300-500 nm, 300-400 nm, 400-1200 nm, 400-1000 nm, 400-800 nm 400-600 nm, 400-500 nm, 500-1200 nm, 500-1000 nm, 500-800 nm, 500-600 nm, 600-1200 nm, 600-1000 nm, 600-800 nm, 600-700 nm, 700-1200 nm, 700-1000 nm, 700-800 nm, 800-1200 nm, 800-1000 nm, 900-1200 nm, 900-1000 nm, 1000-1200 nm and the like, including the range between any two of the above values. In the present invention, the average pore diameter of the SiO2 microsphere support is determined according to GB / T 21650.1-2008 (Determination of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption methods - Part 1: Mercury intrusion porosimetry method) measured using a fully automated high-performance mercury porosimeter AutoPore IV 9500 from Micromeritics Instrument Corporation, USA.

[0030] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the SiO2 microsphere support has a specific surface area of ​​30-200 m². 2 / g. For example, but not limited to, 30-150 m 2 / g, 30-120 m 2 / g, 30-100 m 2 / g, 30-90 m 2 / g, 30-80 m 2 / g, 30-70 m 2 / g, 30-60 m 2 / 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 / g and the like, including the range between any two of the above-mentioned values. In the present invention, the specific surface area of ​​the SiO2 microsphere support is measured according to GB / T 21650.1-2008 (Determination of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption methods - Part 1: Mercury intrusion porosimetry method) using a fully automated high-performance mercury porosimeter AutoPore IV 9500 from Micromeritics Instrument Corporation, USA.

[0031] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the composite oxide treated with the quaternary ammonium salt has such surface properties that its IR spectrum exhibits three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 The IR spectrum can be measured under the following conditions: A Nicolet iS50 IR spectrometer is used, sample preparation and scanning are performed in attenuated total reflection mode, and the scan range is 4000-400 cm⁻¹. -1 The resolution is 4 cm -1 and the number of scans is 32.

[0032] In the present invention, the SiO2 microsphere carrier can be commercially available (e.g. from Shandong Bangkai Materials Co., Ltd., J&K Scientific, Shanghai Aladdin Biochemical Technology Co., Ltd., etc.) or manufactured in-house.

[0033] In some embodiments of the manufacturing process of the 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 or titanium tetrachloride can be dissolved in water; metatitanic acid can be dissolved in a dilute sulfuric acid solution; or tetrabutyl titanate can be dissolved in an ethanol solution.

[0034] In some embodiments of the manufacturing process for the 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 manufacturing process of the 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 0.1-1.0 mol / l. For example, but not limited to, 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 and the like, including the range between any two of the above values.

[0036] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the molar ratio of the SiO2 microsphere support to the group IVB metal-containing compound is 3-40:1, e.g. 4-26:1, 5-30:1, 6-39:1, wherein the amount of the SiO2 microsphere support is calculated as Si and the amount of the titanium-containing compound and / or zirconium-containing compound is calculated as titanium and / or zirconium elements.

[0037] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the conditions for the first impregnation include: a temperature of 20-60 °C and a time of 0.5-8 h.

[0038] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the conditions for the first drying include: a temperature of 105-130 °C and a time of 2-8 h.

[0039] In some embodiments of the manufacturing process of the composite oxide support according to the present invention, the conditions for the first roasting include: a temperature of 450-650 °C and a time of 3-8 h.

[0040] A third aspect of the present invention is to provide a supported catalyst comprising: the above-mentioned composite oxide support and an active component Cu and its oxide applied to the support; the particle size of the copper atom clusters of the active component is not larger than 5 nm; based on the total weight of the supported catalyst, the content of Cu and its oxide, calculated as CuO, is 5-25 wt.%, preferably 8-25 wt.%, more preferably 10-25 wt.% and even more preferably 12-25 wt.%.

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

[0042] In some embodiments of the supported catalyst according to the present invention, the supported catalyst has an average pore diameter of 100-1200 nm. For example, but not limited to, 100-1000 nm, 100-800 nm, 100-600 nm, 100-500 nm, 100-400 nm, 100-300 nm, 100-200 nm, 200-1200 nm, 200-1000 nm, 200-800 nm, 200-600 nm, 200-500 nm, 200-400 nm, 200-300 nm, 300-1200 nm, 300-1000 nm, 300-800 nm, 300-600 nm, 300-500 nm, 300-400 nm, 400-1200 nm, 400-1000 nm, 400-800 nm, 400-600 nm, 400-500 nm, 500-1200 nm, 500-1000 nm, 500-800 nm, 500-600 nm, 600-1200 nm, 600-1000 nm, 600-800 nm, 600-700 nm, 700-1200 nm, 700-1000 nm, 700-800 nm, 800-1200 nm, 800-1000 nm, 900-1200 nm, 900-1000 nm, 1000-1200 nm and the like, including the range between any two of the above The values ​​mentioned. In the present invention, the average pore diameter of the catalyst is determined according to GB / T 21650.1-2008 (Determination of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption methods - Part 1: Mercury intrusion porosimetry method) measured using a fully automated high-performance mercury porosimeter AutoPore IV 9500 from Micromeritics Instrument Corporation, USA.

[0043] In some embodiments of the supported catalyst according to the present invention, the supported catalyst has a specific surface area of ​​30-200 m². 2 / g. For example, but not limited to, 30-150 m 2 / g, 30-120 m 2 / g, 30-100 m 2 / g, 30-90 m 2 / g, 30-80 m 2 / g, 30-70 m 2 / g, 30-60 m 2 / 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 / g and the like, including the range between any two of the above-mentioned values. In the present invention, the specific surface area of ​​the catalyst is measured according to GB / T 21650.1-2008 (Determination of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption methods - Part 1: Mercury intrusion porosimetry method) using a fully automated high-performance mercury porosimeter AutoPore IV 9500 from Micromeritics Instrument Corporation, USA.

[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 2-5 nm, which is characterized by transmission electron microscopy (TEM) and measured using the scale bar.

[0045] In some embodiments of the supported catalyst according to the present invention, the supported catalyst is essentially free of precious metals such as rhodium, palladium, ruthenium, osmium, platinum, and iridium. The expression "essentially free of" means that the content of precious metals (e.g., rhodium, palladium, ruthenium, osmium, platinum, and iridium) in the supported catalyst is less than 1 wt.%, preferably less than 0.5 wt.%, preferably less than 0.2 wt.%, preferably less than 0.1 wt.%, and preferably 0 wt.%. 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 essentially free of non-precious metals (such as cobalt, nickel, molybdenum, zinc, and iron) except for copper, titanium, and zirconium. The expression "essentially free of" means that the content of non-precious metals (such as cobalt, nickel, molybdenum, zinc, and iron) except for copper, titanium, and zirconium in the supported catalyst is less than 1 wt.%, preferably less than 0.5 wt.%, preferably less than 0.2 wt.%, preferably less than 0.1 wt.%, and preferably 0 wt.%. Preferably, the supported catalyst is completely free of non-precious metals (such as cobalt, nickel, molybdenum, zinc, and iron) except for copper, titanium, and zirconium.

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

[0048] A fourth aspect of the present invention consists in providing a method for producing the aforementioned supported catalyst, 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 manufacturing process of the supported catalyst according to the present invention, the molar ratio of the composite oxide support to the soluble copper salt is 1:0.03-0.6, for example 1:0.03-0.4, 1:0.04-0.25, 1:0.05-0.32 or 1:0.06-0.5. The molar amount of the composite oxide support is calculated as Si, and the soluble copper salt is calculated as Cu element.

[0050] In some embodiments of the manufacturing process of the 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 manufacturing process of the supported catalyst according to the present invention, the conditions for the second impregnation include: a temperature of 20-60 °C and a time of 0.5-8 h.

[0052] In some embodiments of the manufacturing process of the supported catalyst according to the present invention, the conditions for the second drying include: a temperature of 105-180 °C and a time of 2-8 h.

[0053] In some embodiments of the manufacturing process of the supported catalyst according to the present invention, the conditions for the second roasting include: a temperature of 450-650 °C and a time of 3-8 h.

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

[0055] In some embodiments of the manufacturing process of the 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 such that, based on the total weight of the supported catalyst, the CuO content calculated as CuO is 5-25 wt.%. For example, but not limited to, 5-20 wt.%, 5-15 wt.%, 5-10 wt.%, 10-25 wt.%, 10-20 wt.%, 10-15 wt.%, 12-25 wt.%, 12-20 wt.%, 12-15 wt.%, 15-25 wt.%, 15-20 wt.%, 20-25 wt.%, and the like.

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

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

[0058] In particular, catalysts with ruthenium carbene complexes of transition metals include, but are not limited to, structures represented by the following formulas (1) to (7):

[0059] The structure of Grubbs catalysts includes, but is not limited to, the structure represented by formula (8):

[0060] In some embodiments of the hydrogenation process for HNBR according to the present invention, the triphenylphosphine chloride is the platinum group metal rhodium triphenylphosphine chloride and / or ruthenium triphenylphosphine chloride.

[0061] In some embodiments of the hydrogenation process for HNBR according to the present invention, the weight ratio of triphenylphosphine to the triphenylphosphine chloride of the platinum group metal is 2-5:1. Examples include, but are not limited to: 2-5:1, 2-4:1 and 2-3:1.

[0062] In some embodiments of the hydrogenation process for HNBR according to the present invention, the weight ratio of the supported catalyst to the homogeneous catalyst is 1:0.01-0.3. Examples include, but are not limited to: 1:0.05-0.3, 1:0.1-0.3, 1:0.15-0.3, 1:0.16-0.3 and the like.

[0063] A sixth aspect of the present invention is to provide a hydrogenation process for a polymer, comprising: dissolving the polymer in an organic solvent, subsequently adding the aforementioned catalyst composition, and reacting the polymer with hydrogen in the presence of the catalyst composition. The hydrogenation process is typically carried out in a reactor, wherein the polymer dissolved in the organic solvent is first placed in the reactor, then the catalyst composition is added, the reactor is subsequently sealed, and hydrogen is introduced to displace air, thus enabling the polymer to react with hydrogen in the presence of the catalyst composition.

[0064] In some embodiments of the hydrogenation process for the polymer according to the present invention, the amount of the supported catalyst constitutes 5-20 wt.% of the polymer, for example 5-20 wt.%, 5-15 wt.%, 5-10 wt.%, 10-20 wt.%, 10-15 wt.%, 15-20 wt.% and the like.

[0065] In some embodiments of the hydrogenation process for the polymer according to the present invention, the reaction conditions include: a temperature of 30-90 °C, a hydrogen pressure of 5-10 MPa and a time of 5-10 h.

[0066] In some embodiments of the hydrogenation process for the polymer 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 0.1-10 wt.%, for example 0.1-10 wt.%, 0.1-8 wt.%, 0.1-6 wt.%, 0.1-4 wt.%, 0.1-2 wt.%, 0.1-1 wt.%, 0.5-10 wt.%, 0.5-8 wt.%, 0.5-6 wt.%, 0.5-4 wt.%, 0.5-2 wt.%, 0.5-1 wt.%, 1-10 wt.%, 1-8 wt.%, 1-6 wt.%, 1-4 wt.%, 1-2 wt.%, 3-10 wt.%, 3-8 wt.%, 3-6 wt.%, 3-4 wt.%, 5-10 wt.%, 5-8 wt.%, 5-6 wt.%, 7-10 wt.%, 7-8 wt.%, 8-10 wt.%, 9-10 wt.% and the like, based on the total weight of the polymer and the solvent.

[0067] In some embodiments of the hydrogenation process for the polymer 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, piperylene, 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.

[0068] In some embodiments of the hydrogenation process for the polymer according to the present invention, the polymer is NBR. In the field, NBR refers to a copolymer polymerized from acrylonitrile and butadiene monomers.

[0069] In some embodiments of the hydrogenation process for the polymer according to the present invention, there are no particular restrictions regarding the type of NBR; that is, the hydrogenation process of the present invention can be used for the hydrogenation of almost all types of NBR. For example, NBR is commercially available (e.g., from Zeon Corporation, with types 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 it can be produced in-house.

[0070] For example, the acrylonitrile content of NBR can be 15-55 wt.%, for example 19-51 wt.%, 20-55 wt.%, 25-55 wt.%, 30-55 wt.%, 35-55 wt.%, 40-55 wt.%, 45-55 wt.%, 20-50 wt.%, 25-50 wt.%, 30-50 wt.%, 35-50 wt.%, 40-50 wt.%, 45-50 wt.%, 20-45 wt.%, 25-45 wt.%, 30-45 wt.%, 35-45 wt.%, 40-45 wt.%, 20-40 wt.%, 25-40 wt.%, 30-40 wt.%, 35-40 wt.%, 20-35 wt.%, 25-35 wt.%, 30-35 wt.% 20-25 wt.%, 20-30 wt.% and 25-30 wt.%, including the range between any two of the above values.

[0071] For example, the Mooney viscosity (ML, 100 °C, 1+4) of NBR can be 20-100, for example 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 above values.

[0072] In some embodiments of the hydrogenation process for the polymer 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.

[0073] In some embodiments of the hydrogenation process for the polymer according to the present invention, the aforementioned hydrogenation process for the polymer further comprises: after completion of the reaction, recovery of the supported catalyst by filtration or centrifugation and recovery of the homogeneous catalyst by ion exchange using an ion exchange resin.

[0074] In some embodiments of the hydrogenation process for the polymer 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%, at least 99%. The degree of hydrogenation is measured according to SH / T 1762-2008 / ISO 14558:2000.

[0075] In some embodiments of the hydrogenation process for the polymer 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 IR spectroscopy using a Nicolet 560 FTIR spectrometer from Nicolet Instrument Corporation, USA.

[0076] A seventh aspect of the present invention consists in providing a hydrogenated polymer, preferably HNBR, obtained by the aforementioned hydrogenation process.

[0077] 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%, at least 99%. The degree of hydrogenation is measured according to SH / T 1762-2008 / ISO 14558:2000.

[0078] 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 tensile strength and wear resistance.

[0079] An eighth aspect of the present invention consists in providing applications of the aforementioned composite oxide support, the composite oxide support obtained by the aforementioned manufacturing process of the composite oxide support, the aforementioned supported catalyst, the supported catalyst obtained by the aforementioned manufacturing process of the supported catalyst, the aforementioned catalyst composition, the hydrogenated polymer obtained by the aforementioned hydrogenation process, or the aforementioned hydrogenated polymer in rubber articles or their manufacture, in particular in HNBR articles or their manufacture.

[0080] Advantages of the present invention: (1) By modifying the SiO2 and group IVB metal oxide composite support with an impregnation solution containing an organic cationic quaternary ammonium salt, the dispersion of the active component on the catalyst surface can be significantly improved and the size of the Cu atom clusters of the active component can be limited to a maximum of 5 nm, thereby significantly improving the hydrogenation activity of the catalyst. (2) The supported catalyst prepared on the basis of the composite support of SiO2 and group IVB metal oxide, treated with an organic cationic quaternary ammonium salt, exhibits 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. (3) The synergistic interaction of the supported catalyst of the present invention with a homogeneous catalyst enables the hydrogenation saturation of polymer materials at relatively low temperatures and pressures, and the resulting hydrogenated polymer products (e.g. HNBR) achieve a high degree of hydrogenation. (4) After completion of the reaction, the supported catalyst is recovered by filtration or centrifugation, and the homogeneous catalyst is recovered by ion exchange using an ion exchange resin, ensuring that the supported catalyst can be reused multiple times and that the catalysts are easy to separate and recover. (5) By using the supported catalyst and the hydrogenation process for hydrogenated polymers (e.g., HNBR) according to the present invention, a supported catalyst for the hydrogenation of NBR using non-precious metals as active components is produced for the first time. This avoids the problem of the loss of precious metal active components, further improves the recoverability of the catalyst, and significantly reduces the cost of the catalyst, thereby lowering the production costs of hydrogenated polymers (HNBR). Description of the illustrations Fig. shows the IR spectrum of the composite oxide support in Example 1 of the present invention. Fig. is the TEM image of the supported catalyst A in Example 13 of the present invention. Fig. shows the IR spectrum of the untreated TiO2-SiO2 composite substrate in comparison test example 1. Fig.shows the IR spectrum of the surface-treated SiO2 support in comparison test example 5. Fig. is a comparison diagram of the IR spectra of the carriers in Example 1, Comparison Test Example 1 and Comparison Test Example 5. Detailed description of the invention

[0081] To better understand the present invention, it will be explained in more detail below using examples. These examples serve only for illustration and are not intended to limit the scope of application of the present invention.

[0082] In the following examples and comparisons: (1) SiO2 microbead support was sourced from Shandong Bangkai Materials Co., Ltd. (2) Dimethyldioctadecylammonium chloride was obtained from J&K Scientific with CAS number 61789-80-8. (3) Cetyltrimethylammonium chloride was obtained from J&K Scientific with CAS number 112-02-7. (4) C 12-14-Alkyldimethylethylbenzylammonium chloride was obtained from J&K Scientific with the CAS number 85409-23-0. (5) The content of Cu and its oxides, calculated as CuO, was analyzed using the Optima 8300 ICP atomic emission spectrometer manufactured by Platinum Elmer (PE), USA, in accordance with standard JY / T 0567-2020. (6) The TiO2 content was measured using a spectrophotometer. The principle is as follows: In sulfuric acid solution, Ti reacts 4+ Titanium dioxide reacts with hydrogen peroxide to form a yellow complex. Titanium dioxide reacts with hot sulfuric acid to form titanyl sulfate, which then reacts with hydrogen peroxide to form a stable orange-yellow complex [TiO(H2O2)]. 2- reacted. The measurement was performed at 430 nm using a Unico UV-2100 spectrophotometer. (7) The ZrO2 content was also measured using a spectrophotometer. (8) The IR spectra were measured under the following conditions using a Nicolet iS50 IR spectrometer: Sample preparation and scanning were performed in attenuated total reflection mode, and the scan range was 4000-400 cm. -1 The resolution was 4 cm -1 and the number of scans was 32. (9) TEM characterization conditions: The catalyst was observed using a high-resolution transmission electron microscope Jem-3010 at an accelerating voltage of 200 kV for HR-TEM characterization. Prior to testing, the sample was completely ground into a powder, a small amount of the sample was added to absolute ethanol, and ultrasonically separated in an ultrasonic cleaner (model PS-10, Shenzhen Jiekang Ultrasonic Cleaner Co., Ltd.) for 15–20 minutes. Finally, the suspension was pipetted and continuously dripped onto a microgrid, followed by natural drying. (10) The particle size of the copper atom clusters of the active component was characterized by transmission electron microscopy (TEM) and measured using the scale bar. Example 1

[0083] 85 g SiO2 microsphere carrier (particle size: 20 µm, average pore diameter: 110 nm, specific surface area: 78 m²) 2 / g) were impregnated for 6 h at 25 °C with 420 ml of an aqueous solution of titanium sulfate with a concentration of 0.45 mol / l, the precipitate was dried for 6 h at 110 °C and then roasted for 5 h at 550 °C to obtain a TiO2-SiO2 composite carrier with a TiO2 content of 15 wt.% (and a SiO2 content of 85 wt.%).

[0084] 5 g of dimethyldioctadecylammonium chloride, to which 95 g of o-xylene were added, were mixed uniformly with 10 ml of hydrochloric acid (37 wt%) to prepare an impregnation solution. The TiO₂-SiO₂ composite support was impregnated with the impregnation solution for 2 h at 20 °C and then dried for 12 h at 60 °C to obtain a TiO₂-SiO₂ composite oxide support.

[0085] The resulting composite oxide support was characterized by IR spectroscopy, and its IR spectrum, i.e., the IR spectrum of the surface-treated SiO2-TiO2 composite oxide, is shown in Fig. The IR spectrum shows that the surface properties of the composite oxide support in Example 1 were such that its IR spectrum exhibited three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibited certain characteristics. In particular, the IR spectrum showed characteristic peaks at 620 cm⁻¹. -1, 649 cm -1 and 708 cm -1 as well as characteristic peaks at 2850 cm -1 , 2919 cm -1 and 2955 cm -1 . Example 2

[0086] The fabrication process for 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 were used instead of 420 ml of an aqueous solution of titanium sulfate with a concentration of 0.45 mol / l to obtain a TiO2-SiO2 composite support with a TiO2 content of 25 wt% (and a SiO2 content of 75 wt%).

[0087] 4 g of dimethyldioctadecylammonium chloride, to which 96 g of o-xylene were added, were mixed uniformly with 8 ml of hydrochloric acid (37 wt%) to prepare an impregnation solution. The TiO₂-SiO₂ composite support was impregnated with the impregnation solution for 2 h at 20 °C and then dried for 12 h at 60 °C to obtain a TiO₂-SiO₂ composite oxide support.

[0088] The IR 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 the IR spectrum showed three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibited [unclear]. Example 3

[0089] The fabrication process of the TiO2-SiO2 composite support was the same as in Example 1, except that 398 ml of an aqueous solution of titanium tetrachloride with a concentration of 0.38 mol / l were used instead of 420 ml of an aqueous solution of titanium sulfate with a concentration of 0.45 mol / l to obtain a TiO2-SiO2 composite support with a TiO2 content of 12 wt% (and a SiO2 content of 88 wt%).

[0090] 3 g of dimethyldioctadecylammonium chloride, to which 97 g of o-xylene were added, were mixed uniformly with 7 ml of hydrochloric acid (37 wt%) to prepare an impregnation solution. The TiO₂-SiO₂ composite support was impregnated with the impregnation solution for 2 h at 20 °C and then dried for 12 h at 60 °C to obtain a TiO₂-SiO₂ composite oxide support.

[0091] The IR 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 the IR spectrum showed three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibited [unclear]. Example 4

[0092] The fabrication process of the TiO2-SiO2 composite support was the same as in Example 1, except that 360 ml of an ethanolic tetrabutyl titanate solution with a concentration of 0.63 mol / l were used instead of 420 ml of an aqueous solution of titanium sulfate with a concentration of 0.45 mol / l to obtain a TiO2-SiO2 composite support with a TiO2 content of 18 wt% (and a SiO2 content of 82 wt%).

[0093] 2 g of dimethyldioctadecylammonium chloride, to which 98 g of o-xylene were added, were mixed uniformly with 5 ml of hydrochloric acid (37 wt%) to prepare an impregnation solution. The TiO₂-SiO₂ composite support was impregnated with the impregnation solution for 2 h at 20 °C and then dried for 12 h at 60 °C to obtain a TiO₂-SiO₂ composite oxide support.

[0094] The IR 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 the IR spectrum showed three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibited [unclear]. Example 5

[0095] The fabrication process for the TiO2-SiO2 composite support was the same as in Example 1, except that 123 ml of an ethanolic tetrabutyl titanate solution with a concentration of 0.51 mol / l were used instead of 420 ml of an aqueous solution of titanium sulfate with a concentration of 0.45 mol / l to obtain a TiO2-SiO2 composite support with a TiO2 content of 5 wt% (and a SiO2 content of 95 wt%).

[0096] 1 g of cetyltrimethylammonium chloride, to which 99 g of o-xylene were added, was mixed uniformly with 3 ml of hydrochloric acid (37 wt%) to prepare an impregnation solution. The TiO₂-SiO₂ composite support was impregnated with the impregnation solution for 4 h at 20 °C and then dried for 12 h at 80 °C to obtain a TiO₂-SiO₂ composite oxide support.

[0097] The IR 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 the IR spectrum showed three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibited [unclear]. Example 6

[0098] The manufacturing process for the TiO2-SiO2 composite support was the same as in Example 1, except that instead of roasting for 5 h at 550 °C, roasting for 7 h at 650 °C was carried out to obtain a TiO2-SiO2 composite support with a TiO2 content of 15 wt.% (and a SiO2 content of 85 wt.%).

[0099] 5 g C 12-14Alkyldimethylethylbenzylammonium chloride, to which 95 g of o-xylene were added, was mixed uniformly with 10 ml of hydrochloric acid (37 wt%) to prepare an impregnation solution. The TiO₂-SiO₂ composite support was impregnated with the impregnation solution for 2 h at 40 °C and then dried for 12 h at 100 °C to obtain a TiO₂-SiO₂ composite oxide support.

[0100] The IR 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 the IR spectrum showed three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibited [unclear]. Example 7

[0101] The manufacturing process is the same as in Example 1, except that 420 ml of an aqueous solution of zirconium tetrachloride with a concentration of 0.29 mol / l were used instead of an aqueous solution of titanium sulfate to obtain a ZrO2-SiO2 composite support with a ZrO2 content of 15 wt.% (and a SiO2 content of 85 wt.%).

[0102] 5 g of dimethyldioctadecylammonium chloride, to which 95 g of o-xylene were added, were mixed uniformly with 10 ml of hydrochloric acid (37 wt%) to prepare an impregnation solution. The ZrO₂-SiO₂ composite support was impregnated with the impregnation solution for 2 h at 20 °C and then dried for 12 h at 60 °C to obtain a ZrO₂-SiO₂ composite oxide support.

[0103] The IR 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 the IR spectrum showed three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibited [unclear]. Example 8

[0104] 85 g of SiO2 microsphere carrier material were impregnated with 280 ml of an aqueous titanium sulfate solution with a concentration of 0.45 mol / l for 6 h at 25 °C. The precipitate was dried for 6 h at 110 °C and then roasted for 5 h at 550 °C. After further impregnation with 300 ml of an aqueous zirconium nitrate solution with a concentration of 0.14 mol / l at 25 °C for 4 h, the precipitate was dried at 110 °C for 8 h and then roasted for 6 h at 550 °C.

[0105] Thus, a TiO2-ZrO2-SiO2 composite carrier with a TiO2 content of 10 wt.%, a ZrO2 content of 5 wt.% (and a SiO2 content of 85 wt.%) was obtained.

[0106] 5 g of dimethyldioctadecylammonium chloride, to which 95 g of o-xylene were added, were mixed uniformly with 10 ml of hydrochloric acid (37 wt%) to prepare an impregnation solution. The TiO₂-ZrO₂-SiO₂ composite support was impregnated with the impregnation solution for 2 h at 20 °C and then dried for 12 h at 60 °C to obtain a TiO₂-ZrO₂-SiO₂ composite oxide support.

[0107] The IR 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 the IR spectrum showed three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibited [unclear]. Example 9

[0108] The manufacturing process of the TiO2-SiO2 composite oxide support was the same as in Example 1, except that instead of the SiO2 microsphere support, a SiO2 microsphere support with a particle size of 10 µm, an average pore diameter of 200 nm and a specific surface area of ​​60 m² was used. 2 / g was used.

[0109] The IR 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 the IR spectrum showed three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibited [unclear]. Example 10

[0110] The manufacturing process of the TiO2-SiO2 composite oxide support was the same as in Example 1, except that instead of the SiO2 microsphere support, a SiO2 microsphere support with a particle size of 5 µm, an average pore diameter of 120 nm and a specific surface area of ​​75 m² was used. 2 / g was used.

[0111] The IR 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 the IR spectrum showed three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibited [unclear]. Example 11

[0112] The manufacturing process of the TiO2-SiO2 composite oxide support was the same as in Example 1, except that instead of the SiO2 microsphere support, a SiO2 microsphere support with a particle size of 30 µm, an average pore diameter of 1000 nm and a specific surface area of ​​37 m² was used. 2 / g was used.

[0113] The IR 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 the IR spectrum showed three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibited [unclear]. Example 12

[0114] The manufacturing process of the TiO2-SiO2 composite oxide support was the same as in Example 1, except that the solvent in the impregnation solution was pyridine instead of o-xylene.

[0115] The IR 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 the IR spectrum showed three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibited [unclear]. Example 13

[0116] 100 g of the composite oxide supports prepared in Examples 1 to 12 were impregnated with 500 ml of an aqueous copper nitrate solution containing 5.26–33.33 g Cu (calculated as CuO) at 25 °C for 180 min, followed by drying at 110 °C for 6 h and subsequent roasting at 500 °C for 4 h, to obtain Cu / TiO₂-SiO₂ catalysts (supported catalysts AI, L, M, N, O) with a Cu and its oxide content, calculated as CuO, of 5–25 wt%. Details are given in Table 1.

[0117] The prepared supported catalyst A was characterized by TEM, and the results are presented in Fig. depicted. From Fig. It is evident that the active component was uniformly distributed, the particle size of the atom clusters of the active component was 2-5 nm, and the average particle size was 3.3 nm. Example 13

[0118] 100 g of the composite oxide support prepared in Example 1 were impregnated for 180 min at 20 °C with 500 ml of an aqueous copper nitrate solution containing 32 g Cu, then dried for 6 h at 110 °C and subsequently roasted for 6 h at 600 °C to obtain a Cu / TiO₂-SiO₂ catalyst (supported catalyst J) with a Cu and its oxide content, calculated as CuO, of 24 wt%. Details are given in Table 1. Example 14

[0119] 100 g of the composite oxide support prepared in Example 1 were impregnated for 180 min at 30 °C with 500 ml of an aqueous copper nitrate solution containing 32 g Cu, then dried for 6 h at 110 °C and subsequently roasted for 7 h at 650 °C to obtain a Cu / TiO₂-SiO₂ catalyst (supported catalyst K) with a Cu and its oxide content, calculated as CuO, of 24 wt%. Details are given in Table 1. Table 1 Supported catalyst no. carrier Cu content and its oxide, calculated as CuO (wt%) Particle size of the copper atom clusters of the active component, nm A TiO2-SiO2 (a TiO2 content of 15 wt.%) in Example 1 24 2-5 B TiO2-SiO2 (a TiO2 content of 25 wt.%) in Example 2 18 2-5 C TiO2-SiO2 (a TiO2 content of 12 wt%) in Example 3 14 2-5 D TiO2-SiO2 (a TiO2 content of 18 wt.%) in Example 4 20 2-5 E TiO2-SiO2 (a TiO2 content of 15 wt.%) in Example 1 5 2-5 F TiO2-SiO2 (a TiO2 content of 5 wt.%) in example 5 24 2-5 G TiO2-SiO2 (a TiO2 content of 15 24 2-5 wt.%) in example 6 H ZrO2-SiO2 (a ZrO2 content of 15 wt.%) in example 7 24 2-5 I TiO2-ZrO2-SiO2 (a TiO2 content of 10 wt.%, a ZrO2 content of 5 wt.%) in Example 8 24 2-5 J TiO2-SiO2 (a TiO2 content of 15 wt.%) in Example 1 24 2-5 K TiO2-SiO2 (a TiO2 content of 15 wt.%) in Example 1 24 2-5 L TiO2-SiO2 (a TiO2 content of 15 wt.%) in Example 9 24 2-5 M TiO2-SiO2 (a TiO2 content of 15 wt.%) in Example 10 24 2-5 N TiO2-SiO2 (a TiO2 content of 15 wt.%) in Example 11 24 2-5 O TiO2-SiO2 (a TiO2 content of 15 wt.%) in Example 12 24 2-5

[0120] The particle size, average pore diameter and specific surface area of ​​the supported catalysts AN were measured, and the results are listed in Table 2.

[0121] However: The particle size was measured according to the test method specified in NB / SH / T 0951-2017 using the MS2000 laser particle size analyzer from Malvern.

[0122] The average pore diameter and specific surface area were measured according to GB / T 21650.1-2008 (Determination of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption methods - Part 1: Mercury intrusion porosimetry method) using a fully automated high-performance mercury porosimeter AutoPore IV 9500 from Micromeritics Instrument Corporation, USA. Table 2 Supported catalyst no. Particle size, µm Average pore diameter, nm Specific surface area, m 2 / G A 20 102 47 B 10 100 51 C 5 104 55 D 20 103 54 E 20 102 65 F 22 106 52 G 20 102 55 H 20 103 54 I 20 100 51 J 20 104 51 K 20 104 52 L 10 186 41 M 5 107 46 N 30 983 36 Test example 1

[0123] To 2 l of a 4 wt% solution of NBR in chlorobenzene (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 and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 6 MPa and a reaction time of 8 h, yielding HNBR.

[0124] The degree of hydrogenation of the obtained HNBR was measured according to the method specified in SH / T 1762-2008 / ISO 14558:2000 (for measuring unsaturation). The result showed that the degree of hydrogenation was 95.2%.

[0125] The selectivity of the obtained HNBR was measured by IR spectroscopy using a Nicolet 560 FTIR spectrometer from Nicolet Instrument Corporation, USA. The measurements showed that the intensity of the -CN absorption peak in the IR spectrum did not decrease after hydrogenation, and no absorption peak representing -NH₂ was observed. This indicates that the -CN group remained unchanged before and after the reaction, meaning that -CN was not hydrogenated and the selectivity was 100%. The results demonstrated a selectivity of 100%. Test example 2

[0126] To 2 l of a 4 wt% solution of NBR in chlorobenzene (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 and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 8 MPa and a reaction time of 6 h, yielding HNBR.

[0127] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 96.1% and the selectivity was 100%. Test example 3

[0128] To 2 l of a 4 wt% solution of NBR in chlorobenzene (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 and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 8 MPa and a reaction time of 6 h, yielding HNBR.

[0129] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 93.8% and the selectivity was 100%. Test example 4

[0130] To 2 l of a 3 wt% solution of NBR in chlorobenzene (prepared by dissolving NBR in chlorobenzene) 8 g of the supported catalyst C, 0.5 g of the homogeneous catalyst rhodium triphenylphosphine chloride and 1.2 g of triphenylphosphine were added and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 8 MPa and a reaction time of 6 h, yielding HNBR.

[0131] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 97.1% and the selectivity was 100%. Test example 5

[0132] To 2 l of a 3 wt% solution of NBR in chlorobenzene (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 and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 8 MPa and a reaction time of 6 h, yielding HNBR.

[0133] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 97.6% and the selectivity was 100%. Test example 6

[0134] After completion of the reaction in Test Example 5, the supported catalyst A was recovered by centrifugal separation, stirred, and washed in the organic solvent chlorobenzene for 4 h, then separated by centrifugation. Using the same reaction conditions as in Test Example 5, the catalyst was reintroduced into the reaction system to investigate its catalytic performance for the hydrogenation of NBR. The experiment was performed four times consecutively. The results for the degree of hydrogenation (measured using the method in Test Example 1) and the selectivity (determined by nuclear magnetic resonance: by comparing the content of -CN groups in the raw material and the hydrogenated product) are shown in Table 3. Table 3 Single-use Reused twice Reused three times Reused four times degree of hydrogenation 94,5 % 93,6 % 93,3 % 92,8 % selectivity 100 % 100 % 100 % 100 % Test example 7

[0135] To 2 l of a 4 wt% solution of NBR in chlorobenzene (prepared by dissolving NBR in chlorobenzene) 8 g of the supported catalyst D, 0.4 g of the homogeneous catalyst rhodium triphenylphosphine chloride and 1.0 g of triphenylphosphine were added and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 8 MPa and a reaction time of 6 h, yielding HNBR.

[0136] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 97.6% and the selectivity was 100%. Test example 8

[0137] Following the procedure in test example 1, except that the supported catalyst E was used instead of the supported catalyst A, HNBR was finally obtained.

[0138] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 91.2% and the selectivity was 100%. Test example 9

[0139] Following the procedure in test example 1, except that the supported catalyst F was used instead of the supported catalyst A, HNBR was finally obtained.

[0140] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 94.1% and the selectivity was 100%. Test example 10

[0141] Following the procedure in test example 1, except that the supported catalyst G was used instead of the supported catalyst A, HNBR was finally obtained.

[0142] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 95.1% and the selectivity was 100%. Test example 11

[0143] Following the procedure in test example 1, except that the supported catalyst H was used instead of the supported catalyst A, HNBR was finally obtained.

[0144] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 95.8% and the selectivity was 100%. Test example 12

[0145] Following the procedure in test example 1, except that the supported catalyst I was used instead of the supported catalyst A, HNBR was finally obtained.

[0146] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 95.4% and the selectivity was 100%. Test example 13

[0147] Following the procedure in test example 1, except that the supported catalyst J was used instead of the supported catalyst A, HNBR was finally obtained.

[0148] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 95.7% and the selectivity was 100%. Test example 14

[0149] Following the procedure in test example 1, except that the supported catalyst K was used instead of the supported catalyst A, HNBR was finally obtained.

[0150] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 94.8% and the selectivity was 100%. Test example 15

[0151] Following the procedure in test example 1, except that the supported catalyst L was used instead of the supported catalyst A, HNBR was finally obtained.

[0152] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 95.3% and the selectivity was 100%. Test example 16

[0153] Following the procedure in test example 1, except that the supported catalyst M was used instead of the supported catalyst A, HNBR was finally obtained.

[0154] The obtained HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 95.0% and the selectivity was 100%. Test example 17

[0155] Following the procedure in test example 1, except that the supported catalyst N was used instead of the supported catalyst A, HNBR was finally obtained.

[0156] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 96.1% and the selectivity was 100%. Test example 18

[0157] Using the method from test example 1, but under the following reaction conditions: a temperature of 80 °C, a hydrogen pressure of 6 MPa and a reaction time of 8 h, HNBR was finally obtained.

[0158] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 93.9% and the selectivity was 100%. Test example 19

[0159] Using the method from test example 1, but under the following reaction conditions: a temperature of 70 °C, a hydrogen pressure of 6 MPa and a reaction time of 8 h, HNBR was finally obtained.

[0160] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 91.7% and the selectivity was 100%. Test example 20

[0161] Using the method from test example 1, but under the following reaction conditions: a temperature of 60 °C, a hydrogen pressure of 6 MPa and a reaction time of 8 h, HNBR was finally obtained.

[0162] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 90.2% and the selectivity was 100%. Test example 21

[0163] Using the method from test example 1, but under the following reaction conditions: a temperature of 50 °C, a hydrogen pressure of 6 MPa and a reaction time of 8 h, HNBR was finally obtained.

[0164] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 88.2% and the selectivity was 100%. Test example 22

[0165] To 2 l of a 4 wt% solution of NBR in chlorobenzene (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 and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 6 MPa and a reaction time of 8 h, yielding HNBR.

[0166] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 95.3% and the selectivity was 100%. Test example 23

[0167] To 2 l of a 4 wt% solution of NBR in chlorobenzene (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 and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 6 MPa and a reaction time of 8 h, yielding HNBR.

[0168] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 95.4% and the selectivity was 100%. Test example 24

[0169] To 2 l of a 4 wt% solution of NBR in chlorobenzene (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 and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 6 MPa and a reaction time of 8 h, yielding HNBR.

[0170] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 95.3% and the selectivity was 100%. Test example 25

[0171] To 2 l of a 4 wt% solution of NBR in chlorobenzene (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 and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 6 MPa and a reaction time of 8 h, yielding HNBR.

[0172] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 98.9% and the selectivity was 100%. Test example 26

[0173] To 2 l of a 4 wt% solution of NBR in chlorobenzene (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 and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 95 °C, a hydrogen pressure of 8 MPa and a reaction time of 8 h, yielding HNBR.

[0174] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 91.3% and the selectivity was 100%. Test example 27

[0175] To 2 l of a 4 wt% solution of NBR in chlorobenzene (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 and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 6 MPa and a reaction time of 8 h, yielding HNBR.

[0176] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 95.2% and the selectivity was 100%. Test example 28

[0177] Following the procedure in test example 1, except that the supported catalyst O was used instead of the supported catalyst A, HNBR was finally obtained.

[0178] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 95.7% and the selectivity was 100%. Comparative test example 1

[0179] The untreated TiO2-SiO2 composite oxide support from Example 1 was used, with the IR spectrum, i.e., the IR spectrum of the untreated TiO2-SiO2 composite oxide support, in Fig. is shown.

[0180] The active component was then applied according to the procedure in Example 12, and finally a Cu / TiO2-SiO2 catalyst with a Cu content of 24 wt% was obtained. The particle size of the Cu atom clusters was 20–50 nm.

[0181] HNBR was finally obtained using the procedure in test example 1.

[0182] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the procedures in Test Example 1. The results showed that the degree of hydrogenation was 88.2% and the selectivity was 99%. Comparative test example 2

[0183] Using the TiO2-SiO2 composite oxide support from Example 1, a Ni / ZrO2-SiO2 catalyst with a Ni content of 24 wt% (supported catalyst DB1) was obtained by following the procedure in Example 5, except that a nickel nitrate solution was used instead of a copper nitrate solution. The particle size of the Ni atom clusters was 10-30 nm.

[0184] Following the procedure in test example 1, with the exception that the supported catalyst DB1 was used instead of the supported catalyst A, HNBR was finally obtained.

[0185] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the procedures in Test Example 1. The results showed that the degree of hydrogenation was 78% and the selectivity was 82.5%. Comparative test example 3

[0186] According to the procedure in test example 1, with the exception that only the supported catalyst A was used, the specific process was as follows: To 2 l of a 3 wt% solution of NBR in chlorobenzene (prepared by dissolving NBR in chlorobenzene) 9.4 g of supported catalyst A were added and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 8 MPa and a reaction time of 6 h, yielding HNBR.

[0187] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the procedures in Test Example 1. The results showed that the degree of hydrogenation was 57.6% and the selectivity was 100%. Comparative test example 4

[0188] According to the procedure in test example 5, with the exception that only a homogeneous catalyst was used, the specific process was as follows: To 2 l of a 3 wt% solution of NBR in chlorobenzene (prepared by dissolving NBR in chlorobenzene) 0.4 g of the homogeneous catalyst rhodium triphenylphosphine chloride and 1.0 g of triphenylphosphine were added and a catalytic hydrogenation reaction was carried out in an autoclave to obtain a rubber solution under the following reaction conditions: a temperature of 90 °C, a hydrogen pressure of 8 MPa and a reaction time of 6 h, yielding HNBR.

[0189] The resulting HNBR was analyzed for its degree of hydrogenation and selectivity according to the methods in Test Example 1. The results showed that the degree of hydrogenation was 67.2% and the selectivity was 100%. Comparative test example 5

[0190] 85 g of SiO2 microsphere carrier (particle size: 20 µm, average pore diameter: 110 nm) were used.

[0191] 5 g of dimethyldioctadecylammonium chloride, to which 95 g of o-xylene were added, were mixed uniformly with 10 ml of hydrochloric acid (37 wt%) to prepare an impregnation solution. The SiO2 microsphere support was impregnated with the impregnation solution for 2 h at 20 °C and then dried for 12 h at 60 °C.

[0192] The IR spectrum of the surface-treated SiO2 support is shown in Fig. depicted.

[0193] Out of Fig. and the Fig. , Fig. until Fig.It is evident that after surface treatment of the composite oxide support with an impregnating solution containing an organic cationic quaternary ammonium salt, the surface properties of the surface-treated composite oxide support are such that its IR spectrum exhibits three characteristic peaks in the range of 610-720 cm⁻¹. -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibits. In contrast, neither the IR spectrum of the untreated TiO2-SiO2 composite oxide support nor the IR spectrum of the surface-treated SiO2 support shows three characteristic peaks in the range of 610-720 cm⁻¹. -1 or three characteristic peaks in the range of 2840-2970 cm -1The composite oxide support of the present invention can significantly improve the dispersion of the active component on the catalyst surface and limit the size of the atom clusters of the active component to a maximum of 5 nm, thereby significantly improving the hydrogenation activity of the catalyst.

[0194] Test examples 1-27 and comparative test examples 1-4 show that the present invention, by applying a method of synergistic interaction with homogeneous catalysts, ensures the hydrogenation saturation of polymer materials at relatively low temperatures and pressures, and that the resulting HNBR products achieve a high degree of hydrogenation, and furthermore ensures that the supported catalyst can be reused multiple times and that the catalysts are easy to separate and recover.

[0195] The above are only preferred examples of the present invention. It should be noted that, for those skilled in the art in this field, the technical inspiration provided by the present invention may include other equivalent modifications and improvements, which should also be considered within the scope of protection of the present invention. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited non-patent literature

[0000] GB / T 21650.1-2008 [0018, 0019] GB / T 21650.1-2008 (Determination of pore size distribution and porosity of solid materials by mercury intrusion porosimetry and gas adsorption methods - Part 1: Mercury intrusion porosimetry method [0029, 0030, 0042, 0043, 0122]

Claims

[1] A composite oxide support, characterized by that it comprises SiO2 and a group IVB metal oxide, wherein the group IVB metal oxide is TiO2 and / or ZrO2, wherein the composite oxide support has surface properties such that its IR spectrum has three characteristic peaks in the range of 610-720 cm⁻¹ -1 and three characteristic peaks in the range of 2840-2970 cm -1 exhibits. [2] Composite oxide carrier according to claim 1, characterized by , that the composite oxide support has surface properties such that its IR spectrum shows characteristic peaks at 620 ± 1 cm -1 , 649 ± 1 cm -1 and 708 ± 1 cm -1 exhibits; and / or the composite oxide support has surface properties such that its IR spectrum shows characteristic peaks at 2850 ± 1 cm⁻¹ -1 , 2919 ± 1 cm -1 and 2955 ± 1 cm -1 exhibits. [3] Composite oxide carrier according to claim 1, characterized bythat the composite oxide support is obtained by subjecting a composite oxide support precursor comprising SiO2 and a metal oxide of group IVB to a surface treatment using an impregnation solution containing an organic cationic quaternary ammonium salt, wherein the surface treatment preferably consists of impregnation and drying; wherein the organic cationic quaternary ammonium salt is preferably a C6+ long-chain alkylquaternary ammonium salt, preferably a C6+ long-chain alkylquaternary ammonium halide salt, more preferably at least one selected from dimethyldioctadecylammonium chloride, cetyltrimethylammonium chloride, and C 12-14 -Alkyldimethylethylbenzylammonium chloride is. [4] Composite oxide support according to any one of claims 1-3, characterized bythat, based on the total weight of the composite oxide support, the content of metal oxide of group IVB is 5-25 wt.% and the content of SiO2 is 75-95 wt.%, preferably the content of metal oxide of group IVB is 10-25 wt.% and the content of SiO2 is 75-90 wt.%; and / or the composite oxide support has a particle size of 5-30 µm; and / or has an average pore diameter of 100-1200 nm; and / or a specific surface area of ​​30-200 m² 2 / g [5] A method for producing the composite oxide support according to any one of claims 1-4, characterized by that it includes the following steps: (1) Subjecting a SiO2 microsphere support to a first impregnation with a solution of a group IVB metal compound, followed by a first drying and a first roasting to obtain a composite oxide support precursor, wherein the group IVB metal compound is a titanium-containing compound and / or a zirconium-containing compound; (2) Subjecting the composite oxide support precursor to a surface treatment using an impregnating solution containing an organic cationic quaternary ammonium salt to obtain the composite oxide support. [6] Method according to claim 5, characterized by, that the impregnation solution containing the organic cationic quaternary ammonium salt comprises the organic cationic quaternary ammonium salt, a solvent and an acid; preferably the concentration of the quaternary ammonium salt in the impregnation solution containing the organic cationic quaternary ammonium salt is 0.1-10 wt.%. [7] Method according to claim 6, characterized by , that the organic cationic quaternary ammonium salt is a C6+ long-chain alkylquaternary ammonium salt, preferably a C6+ long-chain alkylquaternary ammonium halide salt, more preferably at least one selected from dimethyldioctadecylammonium chloride, cetyltrimethylammonium chloride, and C 12-14 -Alkyldimethylethylbenzylammonium chloride; 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. [8] Method according to any one of claims 5-7, characterized by that the surface treatment is an impregnation and drying process, preferably including the impregnation conditions: a temperature of 20-60 °C and a time of 0.5-8 h; the drying conditions include: a temperature of 50-120 °C and a time of 2-10 h. [9] Method according to any one of claims 5-8, characterized bythat the SiO2 microsphere carrier has a particle size of 5-30 µm and / or an average pore diameter of 100-1200 nm and / or a specific surface area of ​​30-200 m² 2 / g [10] Method according to any one of claims 5-9, characterized by , that 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 concentration of the titanium-containing compound and / or the zirconium-containing compound in the solution of the titanium-containing compound and / or the zirconium-containing compound is 0.1-1.0 mol / l. [11] Method according to any one of claims 5-10, characterized by, that the molar ratio of the SiO2 microsphere carrier to the group IVB metal-containing compound is 3-40:1; and / or include the conditions for the first impregnation: a temperature of 20-60 °C and a time of 0.5-8 h; and / or include the conditions for the first drying: a temperature of 105-130 °C and a time of 2-8 h; and / or include the conditions for the first roasting: a temperature of 450-650 °C and a time of 3-8 h. [12] A supported catalyst comprising: the composite oxide support according to any one of claims 1-4 and an active component Cu and its oxide applied to the support; wherein the particle size of the copper atom clusters of the active component is not larger than 5 nm; based on the total weight of the supported catalyst, the content of Cu and its oxide, calculated as CuO, is 5-25 wt.%. [13] Supported catalyst according to claim 12, characterized bythat the supported catalyst has a particle size of 5-30 µm and / or an average pore diameter of 100-1200 nm and / or a specific surface area of ​​30-200 m² 2 / g and / or has a particle size of the copper atom clusters of the active component of 2-5 nm. [14] A method for producing the supported catalyst according to claim 12 or 13, comprising the following steps: subjecting the composite oxide support according to one of claims 1-4 or the composite oxide support obtained by the method according to one of claims 5-9 to a second impregnation with a solution of a soluble copper salt, followed by a second drying and a second roasting. [15] Method according to claim 14, characterized by, that the molar ratio of the composite oxide carrier to the soluble copper salt is 1:0.03-0.6; and / or include the conditions for the second impregnation: a temperature of 20-60 °C and a time of 0.5-8 h; and / or include the conditions for the second drying: a temperature of 105-180 °C and a time of 2-8 h; and / or include the conditions for the second roasting: a temperature of 450-650 °C and a time of 3-8 h. [16] Method according to claim 14 or 15, characterized by , 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 according to claim 12 or 13. [18] Catalyst composition according to claim 17, characterized by, that the homogeneous catalyst comprises triphenylphosphine and triphenylphosphine chloride of a platinum group metal; preferably the triphenylphosphine chloride of the platinum group metal rhodium triphenylphosphine chloride and / or ruthenium triphenylphosphine chloride; Preferably, the weight ratio of triphenylphosphine to triphenylphosphine chloride of the platinum group metal is 2-5:

1. [19] Catalyst composition according to claim 17 or 18, characterized by , that the weight ratio of the supported catalyst to the homogeneous catalyst is 1:0.01-0.

3. [20] A hydrogenation process of a polymer, comprising: dissolving the polymer in an organic solvent, subsequently adding the catalyst composition according to one of claims 17-19 and reacting the polymer with hydrogen in the presence of the catalyst composition. [21] Hydrogenation process according to claim 20, characterized bythat the amount of the supported catalyst is 5-20 wt.% of the polymer. [22] Hydrogenation process according to claim 20, characterized by , that the reaction conditions include: a temperature of 30-90 °C, a hydrogen pressure of 5-10 MPa and a time of 5-10 h. [23] Hydrogenation process according to one of claims 20-22, characterized by that the polymer is NBR. [24] Hydrogenation process according to any one of claims 20-23, characterized by , 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 process according to one of claims 20-24, wherein the hydrogenated polymer is preferably HNBR. [26] Use of the composite oxide support according to any one of claims 1-4, the composite oxide support obtained by the process according to any one of claims 5-11, the supported catalyst according to claim 12 or 13, the supported catalyst obtained by the process according to any one of claims 14-16, the catalyst composition according to any one of claims 17-19, the hydrogenated polymer obtained by the hydrogenation process according to any one of claims 20-24 or the hydrogenated polymer according to claim 25 in rubber articles or in their manufacture, in particular in HNBR articles or in their manufacture.

Images