Composite oxide support, supported catalyst, and hydrogenated nitrile butadiene rubber and preparation method therefor and use thereof

Abstract

Disclosed in the present invention are a composite oxide support, a supported catalyst, and a hydrogenated nitrile butadiene rubber and a preparation method therefor and a use thereof. The composite oxide support comprises: SiO2 and a group IVB metal oxide, wherein the group IVB metal oxide is TiO2 and / or ZrO2, and the composite oxide support has the surface characteristics that three characteristic peaks are present in the infrared spectrum within the range of 610-720 cm-1 and another three characteristic peaks are present in the infrared spectrum within the range of 2840-2970 cm-1. The composite oxide support of the present invention can significantly improve the dispersion of active components on the surface of a catalyst and significantly improve the hydrogenation activity of the catalyst. The supported catalyst of the present invention is used in combination with a homogeneous catalyst for hydrogenation saturation of a high molecular polymer material at a low temperature and pressure, and the resulting high molecular polymer (especially hydrogenated nitrile butadiene rubber) product has a high degree of hydrogenation. In addition, the supported catalyst of the present invention can be reused multiple times, thereby improving the recyclability of the catalyst, reducing the preparation costs.

Description

Composite oxide carrier, supported catalyst and hydrogenated nitrile rubber as well as preparation method and application thereof Technical Field

[0001] The present invention relates to a composite oxide carrier and a preparation method thereof, a supported catalyst and a preparation method thereof, and hydrogenated nitrile rubber and a preparation method and application thereof. Background Art

[0002] Nitrile-butadiene rubber (NBR) is a copolymer of acrylonitrile and butadiene monomers. It offers excellent oil resistance, high wear resistance, good heat resistance, and strong adhesion. However, its disadvantages include poor low-temperature resistance, poor odor resistance, low insulation properties, and low elasticity. It is widely used in the manufacture of various oil-resistant rubber products in the automotive, aviation, and petroleum industries.

[0003] Hydrogenated nitrile rubber (HNBR) is produced by catalytically selectively hydrogenating the unsaturated olefin segments of the hydrocarbon chain of nitrile rubber (NBR). Hydrogenated nitrile rubber exhibits excellent properties such as good oil resistance, heat resistance, chemical resistance, odor resistance, high tear resistance, and wear resistance.

[0004] The main method for industrial production of HNBR at this stage is solution hydrogenation, which mainly includes homogeneous hydrogenation and heterogeneous hydrogenation. Homogeneous hydrogenation refers to the process of dispersing the active components of the catalyst in molecular form in a polymer solution and catalyzing the hydrogenation reaction of the polymer under certain reaction conditions. In homogeneous hydrogenation, the reactants and catalyst are evenly mixed, the reaction conditions are easy to control, and the output product has stable performance. However, a common disadvantage of homogeneous solution hydrogenation is the difficulty in separating the catalyst from the product. Although various technologies have been developed, such as using ion exchange resins to ion exchange precious metals, utilizing the complexation of stannous chloride and rhodium catalysts to extract the precious metal rhodium in aqueous phase, and using temperature-controlled phase transfer catalysts, these methods are difficult to completely remove residual precious metal catalysts in the polymer or may produce gels that affect product quality. In addition, the cost of large-scale industrialization is extremely high. The residual precious metals in the hydrogenation product will not only increase production costs and waste precious metal resources, but also accelerate the aging rate of HNBR and affect the polymer's mechanical processing properties.

[0005] Compared to homogeneous hydrogenation catalytic systems, heterogeneous catalytic reaction systems employ supported precious metal catalysts, effectively resolving the problem of catalyst-to-hydrogenation product separation. This not only enables the reuse of precious metal catalysts but also effectively prevents precious metal residues in polymers. Currently, the preparation of supported catalysts relies on traditional impregnation methods, resulting in larger active component particles and significantly reducing the number of active centers. Furthermore, due to the weak interaction between the active component and the support, the precious metals can easily detach and escape from the support surface after vigorous stirring, reducing catalyst availability and impacting the performance of the hydrogenated products. Ruiong Company uses SiO2 as a support to support Pd metal for hydrogenation of nitrile rubber. While the initial hydrogenation degree is over 95%, the catalyst's effectiveness over repeated uses is poor. For example, activity begins to decline after the second use, with a significant drop in activity after the third or fourth use, and the degree of hydrogenation also decreases significantly.

[0006] The use of homogeneous catalytic hydrogenation methods results in a high degree of hydrogenation, but catalyst separation is difficult and the cost is increasing. The use of heterogeneous catalyst hydrogenation methods to saturate high molecular weight polymers does not result in a high enough degree of hydrogenation, and there is a phenomenon of loss of active components during the stirring process in the reactor or the effect of repeated use of the catalyst is poor, resulting in a significant decrease in the degree of hydrogenation. Therefore, it is necessary to develop a catalyst and related use methods that can ensure a high degree of hydrogenation, easy separation and recovery of the catalyst, and multiple use of the heterogeneous catalyst.

[0007] The above catalysts currently all use precious metals such as rhodium, palladium, ruthenium, osmium, platinum, and iridium as active components. The prior art has not yet disclosed a supported heterogeneous nitrile rubber supported catalyst with high activity, high selectivity, and high stability using non-precious metals as active components.

[0008] Summary of the Invention

[0009] In view of the above problems existing in the prior art, the present invention provides a novel composite oxide carrier, the surface characteristics of which are infrared spectrum at 610-720cm -1 There are three characteristic peaks at 2840-2970cm -1There are three characteristic peaks at place, which can significantly improve the dispersion of the active component of catalyst surface, and the control active component atomic cluster is not more than 5nm, thereby significantly improves the hydrogenation activity of catalyst.And novel multifunctional loaded non-precious metal loaded catalyst of the present invention is with SiO2 microspheres as carrier, and non-precious metal is main active component, and particle size is less.Adopt and cooperate with the method for homogeneous catalyst phase, ensure that under lower temperature and pressure, high molecular polymer material hydrogenation is saturated, and the hydrogenated high molecular polymer (for example hydrogenated nitrile butadiene rubber) product that makes has higher hydrogenation degree.And loaded catalyst of the present invention can be repeatedly used, and catalyst combination is separated and recovered easily. More significantly, used non-precious metal to prepare loaded catalyst for active component, avoided the problem that precious metal active component runs off, further improved the recyclability of catalyst, significantly reduced the cost of catalyst, thereby reduced the production cost of hydrogenated high molecular polymer (for example hydrogenated nitrile butadiene rubber).

[0010] The first aspect of the present invention provides a composite oxide carrier, characterized in that it comprises: SiO2 and a Group IVB metal oxide, wherein the Group IVB metal oxide is TiO2 and / or ZrO2, and the surface characteristics of the composite oxide carrier are infrared spectrum at 610-720cm -1 There are three characteristic peaks at 2840-2970cm -1 In the present invention, the infrared spectrum measurement conditions are as follows: using a Nicolet iS50 infrared spectrometer, sample preparation and scanning using attenuated total reflection mode, scanning range: 4000 ~ 400cm -1 , with a resolution of 4cm -1 , scanning times 32 times. For example, as shown in FIG1 , the surface characteristics of the composite oxide support of the present invention are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

[0011] According to some embodiments of the composite oxide support of the present invention, the surface characteristics of the composite oxide support are as follows: -1 There are three characteristic peaks at 2850-2960cm -1 There are three characteristic peaks.

[0012] According to some embodiments of the composite oxide support of the present invention, the surface characteristics of the composite oxide support are as follows: -1 、649±1cm -1 、708±1cm -1There is a characteristic peak at 2850±1cm; and / or, the surface characteristics of the composite oxide support are infrared spectra at 2850±1cm -1 、2919±1cm -1 、2955±1cm -1 There are characteristic peaks.

[0013] According to some embodiments of the composite oxide support of the present invention, the composite oxide support is obtained by surface-treating a composite oxide support precursor of SiO2 and a Group IVB metal oxide using an impregnation solution containing an organic cationic quaternary ammonium salt.

[0014] According to some embodiments of the composite oxide support of the present invention, the organic cationic quaternary ammonium salt is a C6 or longer chain alkyl quaternary ammonium salt, more preferably a C6 or longer chain alkyl halogen quaternary ammonium salt. More preferably, the halogen is Cl, Br or I, more preferably Cl. More preferably, the C6 or longer chain alkyl is C6-C 24 Alkyl, more preferably C8-C 22 Alkyl, more preferably C 10 -C 20 Alkyl, more preferably C 12 -C 18 More preferably, the organic cationic quaternary ammonium salt is selected from dimethyl dioctadecyl ammonium chloride, hexadecyl trimethyl ammonium chloride and C 12-14 -At least one of alkyldimethylethylbenzyl ammonium chloride.

[0015] According to some embodiments of the composite oxide support of the present invention, the surface treatment is impregnation and drying. That is, the entire process of surface treating the composite oxide support precursor with an organic cationic quaternary ammonium salt does not include any high temperature (e.g., above 300°C) treatment steps such as roasting, calcining, or sintering. In the infrared spectrum of the composite oxide support of the present invention, the wavelength of the IR spectrum at 610-720 cm -1 Three characteristic peaks at 620-710 cm -1 Three characteristic peaks at 620±1cm -1 、649±1cm -1 、708±1cm -1 The characteristic peaks at 2840-2970cm are mainly attributed to the vibration of C-halogen (such as C-Cl); -1 Three characteristic peaks at 2850-2960 cm -1 Three characteristic peaks at 2850±1cm -1 、2919±1cm -1 、2955±1cm -1 The characteristic peak at is mainly attributed to CH vibration.

[0016] According to some embodiments of the method for preparing the composite oxide support of the present invention, based on the total weight of the composite oxide support, the content of the Group IVB metal oxide is 5 to 25 wt %, and the content of SiO 2 is 75 to 95 wt %. For example, but not limited to, the content of the Group IVB metal oxide is 5-20 wt%, 5-15 wt%, 5-10 wt%, 10-25 wt%, 10-20 wt%, 10-15 wt%, 12-25 wt%, 12-20 wt%, 12-15 wt%, 15-25 wt%, 15-20 wt%, 20-25 wt%, etc. Correspondingly, the content of SiO2 is 80-95 wt%, 85-95 wt%, 90-95 wt%, 75-90 wt%, 80-90 wt%, 85-90 wt%, 75-88 wt%, 80-88 wt%, 85-88 wt%, 75-85 wt%, 80-85 wt%, 75-80 wt%, etc. Preferably, the content of the Group IVB metal oxide is 10-25 wt%, and the content of SiO2 is 75-90 wt%. Preferably, the content of the Group IVB metal oxide is greater than 10-25% by weight, and the content of SiO2 is 75-90% by weight. Preferably, the content of the Group IVB metal oxide is 11-25% by weight, and the content of SiO2 is 75-89% by weight. Preferably, the content of the Group IVB metal oxide is 12-25% by weight, and the content of SiO2 is 75-88% by weight. Preferably, the content of the Group IVB metal oxide is 15-25% by weight, and the content of SiO2 is 75-85% by weight.

[0017] According to some embodiments of the method for preparing a composite oxide support according to the present invention, if 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.

[0018] According to some embodiments of the method for preparing a composite oxide support according to the present invention, the particle size of the composite oxide support is 5 to 30 μm. For example, but not limited to, 5 to 25 μm, 5 to 20 μm, 5 to 15 μm, 5 to 10 μm, 10 to 30 μm, 10 to 25 μm, 10 to 20 μm, 10 to 15 μm, 15 to 30 μm, 15 to 25 μm, 15 to 20 μm, 20 to 30 μm, 20 to 25 μm, etc., including ranges between any two of the above values. In the present invention, the particle size of the composite oxide support is measured according to the NB / SH / T 0951-2017 test method using a Malvern MS2000 laser particle size analyzer.

[0019] According to some embodiments of the preparation method of the composite oxide support of the present invention, the average pore size of the composite oxide support is 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 ~1000nm, 400~800nm, 400~600nm, 400~500nm, 500~1200nm, 500~1000nm, 500~800nm, 500~600nm, 600~1200nm, 600~1000nm, 600~800nm, 600~700nm, 700~1200nm, 700~1000nm, 700~800nm, 800~1200nm, 800~1000nm, 900~1200nm, 900~1000nm, 1000~1200nm, etc., including ranges between any two of the above values. In the present invention, the average pore size of the composite oxide support is measured according to the first part of the mercury intrusion method of GBT 21650.1-2008 for determining the pore size distribution and porosity of solid materials by mercury intrusion and gas adsorption, using a high-performance fully automatic mercury intrusion instrument of the AutoPore IV 9500 model from Micromeritics Instruments, USA.

[0020] According to some embodiments of the method for preparing the composite oxide support of the present invention, the specific surface area of ​​the composite oxide support is 30-200 m 2 / g. For example, but not limited to 30 to 150 m2 / g, 30~120m 2 / g, 30~100m 2 / g, 30~90m 2 / g, 30~80m 2 / g, 30~70m 2 / g, 30~60m 2 / g, 30~50m 2 / g, 30~40m 2 / g, 50~200m 2 / g, 50~150m 2 / g, 50~120m 2 / g, 50~100m 2 / g, 50~90m 2 / g, 50~80m 2 / g, 50~70m 2 / g, 50~60m 2 / g, 80~200m 2 / g, 80~150m 2 / g, 80~120m 2 / g, 80~100m 2 / g, 80~90m 2 / g, 100~200m 2 / g, 100~150m 2 / g, 100~120m 2 / g, 120~200m 2 / g, 120~150m 2 / g, etc., including the range between any two of the above values. In the present invention, the specific surface area of ​​the composite oxide support is measured according to the mercury intrusion method of the first part of GBT 21650.1-2008 for determining the pore size distribution and porosity of solid materials by mercury intrusion and gas adsorption method, using a high-performance fully automatic mercury intrusion instrument of the AutoPore IV 9500 model from Micromeritics Instruments, USA.

[0021] The second aspect of the present invention provides a method for preparing the composite oxide support, comprising the following steps:

[0022] (1) performing a first impregnation of a SiO2 microsphere support with a solution containing a Group IVB metal compound, followed by a first drying and a first calcination to obtain an oxide composite support precursor, wherein the Group IVB metal compound is a titanium-containing compound and / or a zirconium-containing compound;

[0023] (2) The composite oxide support precursor is surface-treated with an impregnation solution containing an organic cationic quaternary ammonium salt to obtain the composite oxide support.

[0024] According to some embodiments of the method for preparing a composite oxide support of the present invention, the impregnation solution containing an organic cationic quaternary ammonium salt comprises an organic cationic quaternary ammonium salt, a solvent, and an acid.

[0025] According to some embodiments of the method for preparing the composite oxide support of the present invention, the organic cationic quaternary ammonium salt is a C6 or longer chain alkyl quaternary ammonium salt, more preferably a C6 or longer chain alkyl halogen quaternary ammonium salt. More preferably, the halogen is Cl, Br or I, more preferably Cl. More preferably, the C6 or longer chain alkyl is C6-C 24 Alkyl, more preferably C8-C 22 Alkyl, more preferably C 10 -C 20 Alkyl, more preferably C 12 -C 18 More preferably, the organic cationic quaternary ammonium salt is selected from dimethyl dioctadecyl ammonium chloride, hexadecyl trimethyl ammonium chloride and C 12-14 -At least one of alkyldimethylethylbenzyl ammonium chloride.

[0026] According to some embodiments of the method for preparing a composite oxide support according to the present invention, the solvent is selected from at least one of deionized water, methanol, ethanol, acetone, butanone, tetrahydrofuran, o-xylene, p-xylene, and pyridine. Preferably, the solvent is selected from at least one of o-xylene, p-xylene, and pyridine. More preferably, the solvent is o-xylene or pyridine.

[0027] According to some embodiments of the method for preparing a composite oxide support according to the present invention, the acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, and citric acid. Preferably, the acid is hydrochloric acid. More preferably, the concentration of the acid is 1 to 98.3 wt%.

[0028] According to some embodiments of the method for preparing a composite oxide support according to the present invention, the concentration of the quaternary ammonium salt solution in the impregnation solution containing the organic cationic quaternary ammonium salt is 0.1 to 10 wt %. More preferably, the weight ratio of the organic cationic quaternary ammonium salt, solvent, and acid is 1:10 to 19:1 to 3. For example, 1 mL of 37 wt % concentrated hydrochloric acid in the examples weighs 1.18 g.

[0029] According to some embodiments of the preparation method of the composite oxide support of the present invention, the surface treatment is impregnation and drying. Preferably, the conditions for the impregnation include: a temperature of 20 to 60°C and a time of 0.5 to 8 hours; the conditions for the drying include: a temperature of 50 to 120°C and a time of 2 to 10 hours. In the entire process of surface treating the composite oxide support precursor with an organic cationic quaternary ammonium salt, no high-temperature (e.g., above 300°C) treatment steps such as roasting, calcining, or sintering are included. As a result, the organic cationic quaternary ammonium salt and the acid groups (such as 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 the dispersion of the active components.

[0030] In the present invention, the SiO2 microsphere carrier can be simultaneously impregnated with a solution containing a titanium compound and / or a zirconium compound, and then dried and calcined to obtain a composite oxide carrier of SiO2, TiO2 and / or ZrO2; the SiO2 microsphere carrier can also be first impregnated with a solution containing a titanium compound, and then dried and calcined, and then impregnated with a solution containing a zirconium compound, and then dried and calcined to obtain a composite oxide carrier of SiO2, TiO2 and / or ZrO2; the SiO2 microsphere carrier can also be first impregnated with a solution containing a zirconium compound, and then dried and calcined, and then impregnated with a solution containing a titanium compound, and then dried and calcined to obtain a composite oxide carrier of SiO2, TiO2 and / or ZrO2.

[0031] According to some embodiments of the method for preparing a composite oxide support according to the present invention, the particle size of the SiO2 microsphere support is 5 to 30 μm. For example, but not limited to, 5 to 25 μm, 5 to 20 μm, 5 to 15 μm, 5 to 10 μm, 10 to 30 μm, 10 to 25 μm, 10 to 20 μm, 10 to 15 μm, 15 to 30 μm, 15 to 25 μm, 15 to 20 μm, 20 to 30 μm, 20 to 25 μm, etc., including ranges between any two of the above values. In the present invention, the particle size of the SiO2 microsphere support is measured according to the NB / SH / T 0951-2017 test method using a laser particle size analyzer model MS2000 produced by Malvern.

[0032] According to some embodiments of the preparation method of the composite oxide support of the present invention, the average pore size of the SiO2 microsphere support is 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 ~1000nm, 400~800nm, 400~600nm, 400~500nm, 500~1200nm, 500~1000nm, 500~800nm, 500~600nm, 600~1200nm, 600~1000nm, 600~800nm, 600~700nm, 700~1200nm, 700~1000nm, 700~800nm, 800~1200nm, 800~1000nm, 900~1200nm, 900~1000nm, 1000~1200nm, etc., including ranges between any two of the above values. In the present invention, the average pore size of the SiO2 microsphere carrier is measured according to the first part of the mercury intrusion method of GBT 21650.1-2008 for determining the pore size distribution and porosity of solid materials by mercury intrusion and gas adsorption method, and is measured using a high-performance fully automatic mercury intrusion instrument of the AutoPore IV 9500 model from Micromeritics Instruments, USA.

[0033] According to some embodiments of the method for preparing the composite oxide carrier of the present invention, the specific surface area of ​​the SiO2 microsphere carrier is 30-200m 2 / g. For example, but not limited to 30 to 150 m 2 / g, 30~120m 2 / g, 30~100m 2 / g, 30~90m 2 / g, 30~80m 2 / g, 30~70m 2 / g, 30~60m 2 / g, 30~50m 2 / g, 30~40m 2 / g, 50~200m 2 / g, 50~150m 2 / g, 50~120m 2 / g, 50~100m2 / g, 50~90m 2 / g, 50~80m 2 / g, 50~70m 2 / g, 50~60m 2 / g, 80~200m 2 / g, 80~150m 2 / g, 80~120m 2 / g, 80~100m 2 / g, 80~90m 2 / g, 100~200m 2 / g, 100~150m 2 / g, 100~120m 2 / g, 120~200m 2 / g, 120~150m 2 / g, etc., including the range between any two of the above values. In the present invention, the specific surface area of ​​the SiO2 microsphere carrier is measured according to the first part of the mercury intrusion method for determining the pore size distribution and porosity of solid materials by mercury intrusion and gas adsorption method in GBT 21650.1-2008, using a high-performance fully automatic mercury intrusion instrument of the AutoPore IV 9500 model from Micromeritics Instruments, USA.

[0034] According to some embodiments of the method for preparing the composite oxide support of the present invention, the surface characteristics of the composite oxide after the quaternary ammonium salt treatment are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks at the 4000-400 cm-1 infrared spectrometer. -1， Resolution of 4cm -1 , scan times 32 times.

[0035] In the present invention, the silica microsphere carrier can be purchased commercially (eg, from Shandong Bangkai Materials Co., Ltd., Beijing Bailingwei Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., etc.) or prepared in-house.

[0036] According to some embodiments of the method for preparing a composite oxide support according to the present invention, the titanium-containing compound is selected from at least one of titanium sulfate, metatitanic acid, titanium tetrachloride, and tetrabutyl titanate. For example, titanium sulfate or titanium tetrachloride can be dissolved in water. For another example, metatitanic acid can be dissolved in a dilute sulfuric acid solution. For another example, tetrabutyl titanate can be dissolved in an ethanol solution.

[0037] According to some embodiments of the method for preparing the composite oxide support of the present invention, the zirconium-containing compound is selected from at least one of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, and zirconium oxalate. For example, the zirconium compound can be dissolved in water.

[0038] According to some embodiments of the method for preparing a composite oxide support of the present invention, in the solution containing a titanium compound and / or a zirconium compound, the concentration of the titanium compound and / or the zirconium 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, etc., including ranges between any two of the above values.

[0039] According to some embodiments of the method for preparing a composite oxide support according to the present invention, the molar ratio of the SiO2 microsphere support to the Group IVB metal compound is 3 to 40:1, for example, 4 to 26:1, 5 to 30:1, or 6 to 39:1, wherein the molar amount of the SiO2 microsphere support is calculated based on Si, and the amount of the titanium-containing compound and / or the zirconium-containing compound is calculated based on titanium and / or zirconium elements.

[0040] According to some embodiments of the method for preparing a composite oxide support of the present invention, the conditions for the first impregnation include: a temperature of 20 to 60° C. and a time of 0.5 to 8 hours.

[0041] According to some embodiments of the method for preparing a composite oxide support of the present invention, the first drying conditions include: a temperature of 105 to 130° C. and a time of 2 to 8 hours.

[0042] According to some embodiments of the method for preparing a composite oxide support of the present invention, the conditions for the first calcination include: a temperature of 450 to 650° C. and a time of 3 to 8 hours.

[0043] The third aspect of the present invention provides a supported catalyst comprising: the composite oxide support described above, and active components Cu and its oxide supported on the support; the atomic cluster particle size of the active component copper is not greater than 5 nm; and the content of Cu and its oxide calculated as CuO is 5 to 25 wt %, preferably 8 to 25 wt %, preferably 10 to 25 wt %, and preferably 12 to 25 wt %, based on the total weight of the supported catalyst.

[0044] According to some embodiments of the supported catalyst of the present invention, the particle size of the supported catalyst is 5 to 30 μm. For example, but not limited to, 5 to 25 μm, 5 to 20 μm, 5 to 15 μm, 5 to 10 μm, 10 to 30 μm, 10 to 25 μm, 10 to 20 μm, 10 to 15 μm, 15 to 30 μm, 15 to 25 μm, 15 to 20 μm, 20 to 30 μm, 20 to 25 μm, etc., including ranges between any two of the above values. In the present invention, the particle size of the catalyst is measured according to the NB / SH / T0951-2017 test method using a laser particle size analyzer model MS2000 produced by Malvern.

[0045] According to some embodiments of the supported catalyst of the present invention, the average pore size of the supported catalyst is 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 ~1000nm, 400~800nm, 400~600nm, 400~500nm, 500~1200nm, 500~1000nm, 500~800nm, 500~600nm, 600~1200nm, 600~1000nm, 600~800nm, 600~700nm, 700~1200nm, 700~1000nm, 700~800nm, 800~1200nm, 800~1000nm, 900~1200nm, 900~1000nm, 1000~1200nm, etc., including ranges between any two of the above values. In the present invention, the average pore size of the catalyst is measured according to the first part of the mercury intrusion method of GBT 21650.1-2008 for determining the pore size distribution and porosity of solid materials by mercury intrusion and gas adsorption, using a high-performance fully automatic mercury intrusion instrument AutoPore IV 9500 from Micromeritics Instruments, USA.

[0046] According to some embodiments of the supported catalyst of the present invention, the specific surface area of ​​the supported catalyst is 30 to 200 m 2 / g. For example, but not limited to 30 to 150 m 2 / g, 30~120m 2 / g, 30~100m 2 / g, 30~90m 2 / g, 30~80m 2 / g, 30~70m 2 / g, 30~60m 2 / g, 30~50m 2 / g, 30~40m 2 / g, 50~200m 2 / g, 50~150m 2 / g, 50~120m 2 / g, 50~100m 2 / g, 50~90m2 / g, 50~80m 2 / g, 50~70m 2 / g, 50~60m 2 / g, 80~200m 2 / g, 80~150m 2 / g, 80~120m 2 / g, 80~100m 2 / g, 80~90m 2 / g, 100~200m 2 / g, 100~150m 2 / g, 100~120m 2 / g, 120~200m 2 / g, 120~150m 2 / g, etc., including the range between any two values ​​mentioned above. In the present invention, the specific surface area of ​​the catalyst is measured according to the mercury intrusion method of the first part of GBT21650.1-2008 for determining the pore size distribution and porosity of solid materials by mercury intrusion and gas adsorption method, and is measured using a high-performance fully automatic mercury intrusion instrument of the AutoPore IV 9500 model from Micromeritics Instruments, USA.

[0047] According to some embodiments of the supported catalyst of the present invention, the atomic cluster particle size of the active component copper is 2 to 5 nm. The determination method is to characterize it through a transmission electron microscope (TEM) and measure it according to the scale.

[0048] According to some embodiments of the supported catalyst of the present invention, the supported catalyst is substantially free of precious metals such as rhodium, palladium, ruthenium, osmium, platinum, iridium, etc. The term "substantially free" means that the content of precious metals such as rhodium, palladium, ruthenium, osmium, platinum, iridium, etc. in the supported catalyst is less than 1 wt %, preferably less than 0.5 wt %, preferably less than 0.2 wt %, preferably less than 0.1 wt %, and preferably 0%. Preferably, the supported catalyst is completely free of precious metals such as rhodium, palladium, ruthenium, osmium, platinum, iridium, etc.

[0049] According to some embodiments of the supported catalyst of the present invention, the supported catalyst is substantially free of non-noble metals other than copper, titanium, and zirconium, such as cobalt, nickel, molybdenum, zinc, and iron. The term "substantially free" means that the content of non-noble metals other than copper, titanium, and zirconium, such as cobalt, nickel, molybdenum, zinc, and iron, in the supported catalyst is less than 1 wt %, preferably less than 0.5 wt %, preferably less than 0.2 wt %, preferably less than 0.1 wt %, and preferably 0%. Preferably, the supported catalyst is completely free of non-noble metals other than copper, titanium, and zirconium, such as cobalt, nickel, molybdenum, zinc, and iron, etc.

[0050] According to some embodiments of the supported catalyst of the present invention, the supported catalyst is substantially free of metals other than copper, titanium, and zirconium. The term "substantially free" means that the content of metals other than copper, titanium, and zirconium in the supported catalyst is less than 1 wt %, preferably less than 0.5 wt %, preferably less than 0.2 wt %, preferably less than 0.1 wt %, and preferably 0%. Preferably, the supported catalyst is completely free of metals other than copper, titanium, and zirconium.

[0051] The fourth aspect of the present invention provides a method for preparing the above-mentioned supported catalyst, comprising the following steps: performing a second impregnation on the above-mentioned composite oxide support with a solution of a soluble salt of Cu, followed by a second drying and a second calcination.

[0052] According to some embodiments of the method for preparing a supported catalyst according to the present invention, the molar ratio of the composite oxide support to the soluble Cu 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 ratio of the composite oxide support is calculated based on Si, and the soluble Cu salt is calculated based on the Cu element.

[0053] According to some embodiments of the method for preparing a supported catalyst of the present invention, the soluble salt of Cu is selected from at least one of copper chloride, copper sulfate, copper nitrate, copper acetate and disodium copper ethylenediaminetetraacetate (EDTA-Cu-15).

[0054] According to some embodiments of the method for preparing a supported catalyst of the present invention, the conditions for the second impregnation include: a temperature of 20 to 60° C. and a time of 0.5 to 8 hours.

[0055] According to some embodiments of the method for preparing a supported catalyst of the present invention, the second drying conditions include: a temperature of 105 to 180° C. and a time of 2 to 8 hours.

[0056] According to some embodiments of the method for preparing a supported catalyst of the present invention, the conditions for the second calcination include: a temperature of 450 to 650° C. and a time of 3 to 8 hours.

[0057] According to some embodiments of the method for preparing a supported catalyst according to the present invention, the amounts of the SiO2 microsphere carrier and the solution containing the titanium compound are such that, based on the total weight of the prepared composite oxide carrier of SiO2 and TiO2 and / or ZrO2, the content of TiO2 and / or ZrO2 is 5 to 25 wt%, and the content of SiO2 is 75 to 95 wt%.

[0058] According to some embodiments of the method for preparing a supported catalyst according to the present invention, the amount of the soluble salt of Cu for the second impregnation of the composite oxide support of SiO2, TiO2 and / or ZrO2 is such that the content of CuO, calculated as CuO, is 5 to 25 wt% based on the total weight of the supported catalyst, for example, but not limited to, 5 to 20 wt%, 5 to 15 wt%, 5 to 10 wt%, 10 to 25 wt%, 10 to 20 wt%, 10 to 15 wt%, 12 to 25 wt%, 12 to 20 wt%, 12 to 15 wt%, 15 to 25 wt%, 15 to 20 wt%, 20 to 25 wt%, and the like.

[0059] The fifth aspect of the present invention provides a catalyst composition comprising a homogeneous catalyst and the above-mentioned supported catalyst.

[0060] According to some embodiments of the catalyst composition of the present invention, homogeneous catalysts commonly used in the art can be used, such as transition metal ruthenium carbene complexes, Grubbs catalyst (such as a catalyst for olefin metathesis), triphenylphosphine and triphenylphosphine chloride of a platinum group metal. Preferably, the homogeneous catalyst includes triphenylphosphine and triphenylphosphine chloride of a platinum group metal.

[0061] Specifically, the transition metal ruthenium carbene complex catalyst includes but is not limited to the structures of the following formulas (1) to (7):

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

[0063] According to some embodiments of the hydrogenation method of hydrogenated nitrile rubber according to the present invention, the triphenylphosphine chloride of a platinum group metal is triphenylphosphine rhodium chloride and / or triphenylphosphine ruthenium chloride.

[0064] According to some embodiments of the hydrogenation method of hydrogenated nitrile rubber according to the present invention, the weight ratio of triphenylphosphine to triphenylphosphine chloride of a platinum group metal is 2 to 5:1, for example but not limited to 2 to 5:1, 2 to 4:1, 2 to 3:1, etc.

[0065] According to some embodiments of the hydrogenation method of hydrogenated nitrile rubber according to the present invention, the weight ratio of the supported catalyst to the homogeneous catalyst is 1:0.01-0.3, for example but not limited to 1:0.05-0.3, 1:0.1-0.3, 1:0.15-0.3, 1:0.16-0.3, etc.

[0066] A sixth aspect of the present invention provides a method for hydrogenating a polymer, comprising: dissolving the polymer in an organic solvent, then adding the catalyst composition, and reacting the polymer with hydrogen in the presence of the catalyst composition. The hydrogenation method is typically performed in a reactor. First, the polymer dissolved in the organic solvent is added to the reactor, followed by the catalyst composition. The reactor is then closed, and hydrogen is introduced to displace the air, allowing the polymer and hydrogen to react in the presence of the catalyst composition.

[0067] According to some embodiments of the high molecular weight polymer hydrogenation method of the present invention, the amount of the supported catalyst is 5-20 wt% of the high molecular weight polymer, for example, 5-20 wt%, 5-15 wt%, 5-10 wt%, 10-20 wt%, 10-15 wt%, 15-20 wt%, etc.

[0068] According to some embodiments of the high molecular weight polymer hydrogenation method of the present invention, the reaction conditions include: temperature of 30-90° C., hydrogen pressure of 5-10 MPa, and time of 5-10 h.

[0069] According to some embodiments of the high molecular weight polymer hydrogenation method of the present invention, the amount of organic solvent used to dissolve the high molecular weight polymer is such that the content of the high molecular weight polymer in the organic solvent is 0.1 to 10 wt %. For example, 0.1-10wt%, 0.1-8wt%, 0.1-6wt%, 0.1-4wt%, 0.1-2wt%, 0.1-1wt%, 0.5-10wt%, 0.5-8wt%, 0.5-6wt%, 0.5-4wt%, 0.5-2wt%, 0.5-1wt%, 1-10wt%, 1-8wt%, 1-6wt%, 1-4wt%, 1-2wt%, 3-10wt%, 3-8wt%, 3-6wt%, 3-4wt%, 5-10wt%, 5-8wt%, 5-6wt%, 7-10wt%, 7-8wt%, 8-10wt%, 9-10wt%, etc., based on the total weight of the polymer and the solvent.

[0070] According to some embodiments of the high molecular weight polymer hydrogenation method of the present invention, the high molecular weight polymer is an unsaturated copolymer of a conjugated diene and a copolymerizable monomer. The conjugated diene is selected from at least one of butadiene, isoprene, piperylene, and 2,3-dimethylbutadiene, preferably butadiene and / or isoprene, more preferably butadiene. The copolymerizable monomer is selected from at least one of acrylonitrile, methacrylonitrile, styrene, propyl acrylate, butyl acrylate, propyl methacrylate, and butyl methacrylate, preferably acrylonitrile and / or methacrylonitrile, more preferably acrylonitrile.

[0071] According to some embodiments of the high molecular weight polymer hydrogenation method of the present invention, the high molecular weight polymer is nitrile rubber. In the art, nitrile rubber refers to a copolymer formed by polymerization of acrylonitrile and butadiene monomers.

[0072] According to some embodiments of the hydrogenation method of high molecular polymer of the present invention, paracril is not particularly restricted, and promptly hydrogenation method of the present invention almost can be used for the hydrogenation of all paracril.For example, paracril can be by being purchased (for example from Rui Weng Co., Ltd. (such as trade mark 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 Qilu Petrochemical) or self-control acquisition.

[0073] For example, the acrylonitrile content of the nitrile rubber can be 15-55wt%, for example, 19-51wt%, 20-55wt%, 25-55wt%, 30-55wt%, 35-55wt%, 40-55wt%, 45-55wt%, 20-50wt%, 25-50wt%, 30-50wt%, 35-50wt%, 40-50wt%, 45-50wt%, 20- 45wt%, 25-45wt%, 30-45wt%, 35-45wt%, 40-45wt%, 20-40wt%, 25-40wt%, 30-40wt%, 35-40wt%, 20-35wt%, 25-35wt%, 30-35wt%, 20-25wt%, 20-30wt%, 25-30wt%, etc., including ranges between any two of the above values.

[0074] For example, the Mooney viscosity (ML, 100°C, 1+4) of the nitrile rubber can be 20-100, such as 20-40, 20-60, 20-80, 25-35, 25-55, 25-75, 25-95, 30-50, 30-70, 30-90, 35-45, 35-65, 35-85, 40-60, 40-80, 40-100, 45-55, 45-75, 45-95, 50-70, 50-90, 55-65, 55-85, 60-80, 60-100, 65-75, 65-95, 70-90, 75-85, 80-100, 85-95, 90-100, etc., including ranges between any two of the above values.

[0075] According to some embodiments of the high molecular weight polymer hydrogenation method of the present invention, the organic solvent is selected from at least one of chlorobenzene, acetone, butanone, tetrahydrofuran, dichloromethane, chloroform, cyclohexanone, ethyl acetate and dimethylformamide.

[0076] According to some embodiments of the polymer hydrogenation method of the present invention, the polymer hydrogenation method may further include: after the reaction is completed, recovering the supported catalyst by filtration or centrifugation, and recovering the homogeneous catalyst by ion exchange with an ion exchange resin.

[0077] According to some embodiments of the high molecular weight polymer hydrogenation method of the present invention, the degree of hydrogenation is at least 90%, for example, but not limited to, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99%. The degree of hydrogenation is tested according to SH / T 1762-2008 / ISO 14558:2000.

[0078] According to some embodiments of the polymer hydrogenation method of the present invention, the selectivity is at least 98%, for example, but not limited to, at least 99%, at least 99.1%, at least 99.2%, at least 99.3%, at least 99.4%, at least 99.5%, at least 99.6%, at least 99.7%, at least 99.8%, at least 99.9%, or 100%. The selectivity is tested by infrared spectroscopy using a Nicolet 560 Fourier Transform Infrared Spectrometer manufactured by Nicolet Corporation in the United States.

[0079] The seventh aspect of the present invention provides a hydrogenated high molecular polymer obtained by the above-mentioned hydrogenation method, preferably a hydrogenated nitrile rubber.

[0080] According to some embodiments of the hydrogenated high molecular weight polymer of the present invention, preferably hydrogenated nitrile rubber, the degree of hydrogenation of the hydrogenated high molecular weight polymer, preferably hydrogenated nitrile rubber is at least 90%, for example, but not limited to at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%. The test method for the degree of hydrogenation is SH / T 1762-2008 / ISO 14558:2000.

[0081] According to some embodiments of the hydrogenated nitrile rubber of the present invention, the hydrogenated nitrile rubber has excellent characteristics such as good oil resistance, heat resistance, chemical corrosion resistance, odor resistance, high tear resistance and wear resistance.

[0082] The eighth aspect of the present invention provides the above-mentioned composite oxide carrier, the composite oxide carrier obtained by the preparation method of the above-mentioned composite oxide carrier, the above-mentioned loaded catalyst, the loaded catalyst obtained by the preparation method of the above-mentioned loaded catalyst, the above-mentioned catalyst composition, the hydrogenated polymer obtained by the above-mentioned polymer hydrogenation method, or the use of the above-mentioned hydrogenated polymer in rubber products or their manufacture, especially in the field of hydrogenated nitrile rubber products or their manufacture.

[0083] Beneficial effects of the present invention:

[0084] (1) Using an impregnation solution containing an organic cationic quaternary ammonium salt to modify the composite support of SiO2 and Group IVB metal oxide can significantly improve the dispersion of active components on the catalyst surface and control the size of the active component Cu atomic cluster to be no larger than 5nm, thereby significantly improving the hydrogenation activity of the catalyst.

[0085] (2) The supported catalyst is prepared based on a composite carrier of SiO2 treated with organic cationic quaternary ammonium salt and Group IVB metal oxide. The pore structure is suitable for the hydrogenation of macromolecules such as nitrile rubber. The TiO2 and / or ZrO2 on the surface of the carrier can improve the hydrogenation activity of the catalyst. The catalyst has good hydrogenation activity and stability.

[0086] (3) The supported catalyst of the present invention is coordinated with a homogeneous catalyst to achieve hydrogenation saturation of the polymer material at a lower temperature and pressure, and the obtained hydrogenated polymer (such as hydrogenated nitrile rubber) product has a higher degree of hydrogenation.

[0087] (4) After the reaction is completed, the supported catalyst is recovered by filtration or centrifugation, and the homogeneous catalyst is recovered by ion exchange using an ion exchange resin, which can ensure that the supported catalyst can be reused multiple times and the catalyst can be easily separated and recovered.

[0088] (5) The supported catalyst and hydrogenation method of hydrogenated high molecular weight polymer (e.g., hydrogenated nitrile butadiene rubber) of the present invention are used for the first time to prepare a supported catalyst using a non-noble metal as an active component for hydrogenation of nitrile butadiene rubber, thereby avoiding the problem of loss of the noble metal active component, further improving the recyclability of the catalyst, and significantly reducing the cost of the catalyst, thereby reducing the production cost of the hydrogenated high molecular weight polymer (hydrogenated nitrile butadiene rubber). BRIEF DESCRIPTION OF THE DRAWINGS

[0089] FIG1 is an infrared spectrum of the composite oxide support of Example 1 of the present invention.

[0090] FIG2 is a TEM image of supported catalyst A of Example 13 of the present invention.

[0091] FIG3 is an infrared spectrum of the TiO 2 -SiO 2 composite support without surface treatment in Comparative Example 1.

[0092] FIG4 is an infrared spectrum of the surface-treated SiO2 carrier of Comparative Example 5.

[0093] FIG5 is a comparison chart of infrared spectra of the carriers of Example 1, Comparative Test Example 1, and Comparative Test Example 5. DETAILED DESCRIPTION

[0094] In order to make the present invention easier to understand, the present invention will be described in detail below with reference to embodiments. These embodiments are only for illustration and do not limit the scope of application of the present invention.

[0095] In the following examples and comparative examples,

[0096] (1) SiO2 microsphere carriers were purchased from Shandong Bangkai Materials Co., Ltd.

[0097] (2) Dimethyldioctadecyl ammonium chloride, purchased from Beijing Bailingwei Technology Co., Ltd., CAS No. 61789-80-8.

[0098] (3) Hexadecyltrimethylammonium chloride, purchased from Beijing Bailingwei Technology Co., Ltd., CAS No. 112-02-7.

[0099] (4)C 12-14 -Alkyl dimethyl ethyl benzyl ammonium chloride was purchased from Beijing Bailingwei Technology Co., Ltd. with a CAS number of 85409-23-0.

[0100] (5) The content of Cu and its oxides, calculated as CuO, was analyzed using an Optima 8300 ICP atomic emission spectrometer (PE) from PerkinElmer, USA, according to the standard JY / T 0567-2020.

[0101] (6) TiO2 content was determined using a spectrophotometer. The principle used is: in sulfuric acid solution, Ti 4+ It forms a yellow complex with hydrogen peroxide. Titanium dioxide forms titanium sulfate in hot sulfuric acid, and titanium sulfate reacts with hydrogen peroxide to form a stable orange-yellow [TiO(H2O2)] 2- , measured at 430 nm using a Unicol UV-2100 spectrophotometer.

[0102] (7) Similarly, the ZrO2 content was determined using a spectrophotometer.

[0103] (8) Infrared spectra were measured using a Nicolet iS50 infrared spectrometer. Sample preparation and scanning were performed using the attenuated total reflection mode. The scanning range was 4000–400 cm. -1, with a resolution of 4cm -1 , scan times 32 times.

[0104] (9) TEM Characterization Conditions: The catalysts were observed using a Jem-3010 high-resolution transmission electron microscope (HRTEM) at an accelerating voltage of 200 kV. Samples were thoroughly ground into powder before testing. A small amount of the sample was added to anhydrous ethanol and ultrasonically separated for 15–20 min in an ultrasonic cleaner (PS-10, Shenzhen Jiekang Ultrasonic Cleaning Co., Ltd.). Finally, the suspension was pipetted onto the microgrid and allowed to dry naturally.

[0105] (10) The particle size of the active component copper atomic cluster was characterized by transmission electron microscopy (TEM) and measured according to the scale.

[0106] [Example 1]

[0107] Take SiO2 microsphere carrier (particle size 20μm, average pore size 110nm, specific surface area 78m 2 85 g of sintered aluminum (1000 wt%) was impregnated with 420 mL of a 0.45 mol / L titanium sulfate aqueous solution at 25°C for 6 h. The precipitate was dried at 110°C for 6 h and calcined at 550°C for 5 h. This produced a TiO2-SiO2 composite support (SiO2 content of 85 wt%) with a TiO2 content of 15 wt%.

[0108] Take 5g of dimethyldioctadecylammonium chloride, add 95g of o-xylene, and mix evenly with 10mL of hydrochloric acid (mass fraction 37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at 20°C. After impregnation for 2h, dry it at 60°C for 12h to obtain a TiO2-SiO2 composite oxide support.

[0109] The prepared composite oxide support was characterized by infrared spectroscopy. The infrared spectrum is shown in Figure 1, which is the infrared spectrum of the SiO2-TiO2 composite oxide after surface treatment. It can be seen from the infrared spectrum that the surface characteristics of the composite oxide support of Example 1 are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks at 620 cm -1 、649cm -1 、708cm -1 There are characteristic peaks at 2850cm -1 、2919cm -1 、2955cm -1 There are characteristic peaks.

[0110] [Example 2]

[0111] The preparation method of the TiO2-SiO2 composite carrier is the same as that in Example 1, except that 420 mL of an aqueous solution of titanium sulfate with a concentration of 0.45 mol / L is replaced by 420 mL of a dilute sulfuric acid solution of titanic acid with a concentration of 0.86 mol / L to obtain a TiO2-SiO2 composite carrier with a TiO2 content of 25 wt% (SiO2 content of 75 wt%).

[0112] Take 4g of dimethyldioctadecylammonium chloride, add 96g of o-xylene, and mix evenly with 8mL of hydrochloric acid (mass fraction 37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at 20°C. After impregnation for 2h, dry it at 60°C for 12h to obtain a TiO2-SiO2 composite oxide support.

[0113] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1. The surface characteristics are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

[0114] [Example 3]

[0115] The preparation method of the TiO2-SiO2 composite carrier is the same as that in Example 1, except that 420 mL of an aqueous solution of titanium sulfate with a concentration of 0.45 mol / L is replaced by 398 mL of an aqueous solution of titanium tetrachloride with a concentration of 0.38 mol / L to obtain a TiO2-SiO2 composite carrier with a TiO2 content of 12 wt% (SiO2 content is 88 wt%).

[0116] Take 3g of dimethyldioctadecylammonium chloride, add 97g of o-xylene, and mix evenly with 7mL of hydrochloric acid (mass fraction 37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at 20°C. After impregnation for 2h, dry it at 60°C for 12h to obtain a TiO2-SiO2 composite oxide support.

[0117] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1. The surface characteristics are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

[0118] [Example 4]

[0119] The preparation method of the TiO2-SiO2 composite carrier is the same as that in Example 1, except that 420 mL of an aqueous solution of titanium sulfate with a concentration of 0.45 mol / L is replaced by 360 mL of an ethanol solution of tetrabutyl titanate with a concentration of 0.63 mol / L to obtain a TiO2-SiO2 composite carrier with a TiO2 content of 18 wt% (SiO2 content is 82 wt%).

[0120] Take 2g of dimethyldioctadecylammonium chloride, add 98g of o-xylene, and mix evenly with 5mL of hydrochloric acid (mass fraction 37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at 20°C. After impregnation for 2h, dry it at 60°C for 12h to obtain a TiO2-SiO2 composite oxide support.

[0121] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1. The surface characteristics are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

[0122] [Example 5]

[0123] The preparation method of the TiO2-SiO2 composite carrier is the same as that in Example 1, except that 420 mL of an aqueous solution of titanium sulfate with a concentration of 0.45 mol / L is replaced by 123 mL of an ethanol solution of tetrabutyl titanate with a concentration of 0.51 mol / L to obtain a TiO2-SiO2 composite carrier with a TiO2 content of 5 wt% (SiO2 content is 95 wt%).

[0124] Take 1g of hexadecyltrimethylammonium chloride, add 99g of o-xylene, and mix evenly with 3mL of hydrochloric acid (mass fraction 37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at 20°C. After impregnation for 4h, dry it at 80°C for 12h to obtain a TiO2-SiO2 composite oxide support.

[0125] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1. The surface characteristics are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

[0126] [Example 6]

[0127] The preparation method of the TiO2-SiO2 composite support was the same as that of Example 1, except that the calcination at 550°C for 5 h was replaced by calcination at 650°C for 7 h. A TiO2-SiO2 composite support with a TiO2 content of 15 wt% (SiO2 content of 85 wt%) was obtained.

[0128] Take 5g of C 12-14 -alkyl dimethyl ethyl benzyl ammonium chloride, add 95g of o-xylene, and mix evenly with 10mL of hydrochloric acid (mass fraction 37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-SiO2 composite support at 40°C. After impregnation for 2h, dry it at 100°C for 12h to obtain a TiO2-SiO2 composite oxide support.

[0129] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1. The surface characteristics are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

[0130] [Example 7]

[0131] The method of Example 1 was followed, except that the aqueous solution of titanium sulfate was replaced with 420 mL of an aqueous solution of zirconium tetrachloride having a concentration of 0.29 mol / L, to obtain a ZrO2-SiO2 composite support. The resulting ZrO2-SiO2 composite support had a ZrO2 content of 15 wt% (SiO2 content of 85 wt%).

[0132] Take 5g of dimethyldioctadecylammonium chloride, add 95g of o-xylene, and mix evenly with 10mL of hydrochloric acid (mass fraction 37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the ZrO2-SiO2 composite support at 20°C. After impregnation for 2h, dry it at 60°C for 12h to obtain a ZrO2-SiO2 composite oxide support.

[0133] The infrared spectrum of the obtained ZrO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1. The surface characteristics are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

[0134] [Example 8]

[0135] 85 g of SiO2 microsphere carrier was impregnated with 280 mL of a 0.45 mol / L titanium sulfate aqueous solution at 25°C for 6 hours. The precipitate was dried at 110°C for 6 hours and calcined at 550°C for 5 hours. The carrier was then impregnated with 300 mL of a 0.14 mol / L zirconium nitrate aqueous solution at 25°C for 4 hours. The precipitate was dried at 110°C for 8 hours and calcined at 550°C for 6 hours.

[0136] A TiO2-ZrO2-SiO2 composite carrier (SiO2 content is 85wt%) with a TiO2 content of 10wt% and a ZrO2 content of 5wt% was prepared.

[0137] Take 5g of dimethyldioctadecylammonium chloride, add 95g of o-xylene, and mix evenly with 10mL of hydrochloric acid (mass fraction 37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the TiO2-ZrO2-SiO2 composite support at 20°C. After impregnation for 2h, dry it at 60°C for 12h to obtain a TiO2-ZrO2-SiO2 composite oxide support.

[0138] The infrared spectrum of the obtained TiO2-ZrO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1. The surface characteristics are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

[0139] [Example 9]

[0140] The preparation method of TiO2-SiO2 composite oxide carrier is the same as that in Example 1, except that the SiO2 microsphere carrier is replaced with a carrier having a particle size of 10 μm, an average pore size of 200 nm, and a specific surface area of ​​60 m 2 / g SiO2 microsphere carrier.

[0141] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1. The surface characteristics are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

[0142] [Example 10]

[0143] The preparation method of TiO2-SiO2 composite oxide carrier is the same as that in Example 1, except that the SiO2 microsphere carrier is replaced by a carrier with a particle size of 5 μm, an average pore size of 120 nm, and a specific surface area of ​​75 m 2 / g SiO2 microsphere carrier.

[0144] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1. The surface characteristics are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

[0145] [Example 11]

[0146] The preparation method of TiO2-SiO2 composite oxide carrier is the same as that in Example 1, except that the SiO2 microsphere carrier is replaced by a carrier having a particle size of 30 μm, an average pore size of 1000 nm, and a specific surface area of ​​37 m 2 / g SiO2 microsphere carrier.

[0147] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1. The surface characteristics are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

[0148] [Example 12]

[0149] The preparation method of the TiO2-SiO2 composite oxide support is the same as that of Example 1, except that the solvent in the impregnation solution is replaced by pyridine instead of o-xylene.

[0150] The infrared spectrum of the obtained TiO2-SiO2 composite oxide support is similar to that of the composite oxide support in Example 1. The surface characteristics are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

[0151] [Example 13]

[0152] 100 g of each composite oxide support prepared in Examples 1-12 was added to 500 mL of an aqueous solution of copper nitrate containing 5.26 to 33.33 g of Cu (calculated as CuO). The solution was immersed at 25°C for 180 minutes, dried at 110°C for 6 hours, and then calcined at 500°C for 4 hours to produce Cu / TiO2-SiO2 catalysts (supported catalysts A1, L, M, N, and O) having a Cu and its oxide content of 5 to 25 wt% (calculated as CuO). The details are shown in Table 1.

[0153] The prepared supported catalyst A was subjected to TEM characterization, and the results are shown in FIG2 . As can be seen from FIG2 , the active components are uniformly dispersed, the atomic cluster particle size of the active components is 2 to 5 nm, and the average particle size is 3.3 nm.

[0154] [Example 13]

[0155] 100 g of the composite oxide support prepared in Example 1 was added to 500 mL of an aqueous solution of copper nitrate containing 32 g of Cu, immersed at 20° C. for 180 minutes, dried at 110° C. for 6 hours, and then calcined at 600° C. for 6 hours to produce a Cu / TiO2-SiO2 catalyst (supported catalyst J) having a Cu and its oxide content of 24 wt% calculated as CuO. The details are shown in Table 1.

[0156] [Example 14]

[0157] 100 g of the composite oxide support prepared in Example 1 was added to 500 mL of an aqueous solution of copper nitrate containing 32 g of Cu, immersed at 30° C. for 180 minutes, dried at 110° C. for 6 hours, and then calcined at 650° C. for 7 hours to produce a Cu / TiO2-SiO2 catalyst (supported catalyst K) having a Cu and its oxide content of 24 wt% calculated as CuO. The details are shown in Table 1.

[0158] Table 1

[0159] The particle size, average pore size, and specific surface area of ​​the supported catalyst AN were tested, and the results are shown in Table 2.

[0160] The average particle size was measured according to the NB / SH / T 0951-2017 test method using a laser particle size analyzer model MS2000 produced by Malvern.

[0161] The average pore size and specific surface area were determined according to the first part of the mercury intrusion method of GBT 21650.1-2008 for the determination of pore size distribution and porosity of solid materials by mercury intrusion and gas adsorption method, using a high-performance fully automatic mercury intrusion instrument AutoPore IV 9500 from Micromeritics Instruments, USA.

[0162] Table 2

[0163] Test Example 1

[0164] Take 2L of 4wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 8g of supported catalyst A, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.0g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 6MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0165] The obtained hydrogenated nitrile rubber was tested for its degree of hydrogenation using the test method SH / T 1762-2008 / ISO14558:2000 (measurement of unsaturation). The result showed that the degree of hydrogenation was 95.2%.

[0166] The resulting hydrogenated nitrile rubber was tested for selectivity using infrared spectroscopy using a Nicolet 560 Fourier transform infrared spectrometer (made by Nicolet, USA). The absorption peak intensity for -CN in the spectrum remained unchanged after hydrogenation, and no absorption peak representing -NH2 appeared. This indicates that -CN remained unchanged before and after the reaction, indicating that -CN was not hydrogenated, resulting in a selectivity of 100%. The results showed a selectivity of 100%.

[0167] Test Example 2

[0168] Take 2L of 4wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 8g of supported catalyst A, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.0g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0169] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 96.1% and the selectivity was 100%.

[0170] Test Example 3

[0171] Take 2L of 4wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 8g of supported catalyst B, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.0g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0172] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 93.8% and the selectivity was 100%.

[0173] Test Example 4

[0174] Take 2L of 3wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 8g of supported catalyst C, 0.5g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.2g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0175] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 97.1% and the selectivity was 100%.

[0176] Test Example 5

[0177] Take 2L of 3wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 8g of supported catalyst A, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.0g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0178] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 97.6% and the selectivity was 100%.

[0179] Test Example 6

[0180] After the reaction in Test Example 5, supported catalyst A was recovered by centrifugation, washed with stirring in chlorobenzene for 4 h, and then centrifuged. Using the same reaction conditions as in Test Example 5, it was re-added to the reaction system to investigate its NBR hydrogenation catalytic performance. Four consecutive experiments were conducted. The results of the hydrogenation degree (tested according to the method of Test Example 1) and selectivity (NMR measurement: comparing the CN group content in the raw material and the hydrogenated product) are listed in Table 3.

[0181] Table 3

[0182] Test Example 7

[0183] Take 2L of 4wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 8g of supported catalyst D, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.0g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0184] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 97.6% and the selectivity was 100%.

[0185] Test Example 8

[0186] The method of Test Example 1 was followed, except that supported catalyst A was replaced by supported catalyst E, to finally obtain hydrogenated nitrile rubber.

[0187] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 91.2% and the selectivity was 100%.

[0188] Test Example 9

[0189] The method of Test Example 1 was followed, except that supported catalyst A was replaced by supported catalyst F, to finally obtain hydrogenated nitrile rubber.

[0190] The hydrogenation degree of the obtained hydrogenated nitrile rubber was tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 94.1% and the selectivity was 100%.

[0191] Test Example 10

[0192] The method of Test Example 1 was followed, except that supported catalyst A was replaced by supported catalyst G, to finally obtain hydrogenated nitrile rubber.

[0193] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 95.1% and the selectivity was 100%.

[0194] Test Example 11

[0195] The method of Test Example 1 was followed, except that the supported catalyst A was replaced by the supported catalyst H, to finally obtain hydrogenated nitrile rubber.

[0196] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 95.8% and the selectivity was 100%.

[0197] Test Example 12

[0198] The method of Test Example 1 was followed, except that supported catalyst A was replaced by supported catalyst I, to finally obtain hydrogenated nitrile rubber.

[0199] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 95.4% and the selectivity was 100%.

[0200] Test Example 13

[0201] The method of Test Example 1 was followed, except that supported catalyst A was replaced by supported catalyst J, to finally obtain hydrogenated nitrile rubber.

[0202] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 95.7% and the selectivity was 100%.

[0203] Test Example 14

[0204] The method of Test Example 1 was followed, except that supported catalyst A was replaced by supported catalyst K, to finally obtain hydrogenated nitrile rubber.

[0205] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 94.8% and the selectivity was 100%.

[0206] Test Example 15

[0207] The method of Test Example 1 was followed, except that supported catalyst A was replaced by supported catalyst L, to finally obtain hydrogenated nitrile rubber.

[0208] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 95.3% and the selectivity was 100%.

[0209] Test Example 16

[0210] The method of Test Example 1 was followed, except that the supported catalyst A was replaced by the supported catalyst M, to finally obtain hydrogenated nitrile rubber.

[0211] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 95.0% and the selectivity was 100%.

[0212] Test Example 17

[0213] The method of Test Example 1 was followed, except that supported catalyst A was replaced by supported catalyst N, to finally obtain hydrogenated nitrile rubber.

[0214] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 96.1% and the selectivity was 100%.

[0215] Test Example 18

[0216] The method of Test Example 1 was followed, except that the reaction conditions were: temperature 80° C., hydrogen pressure 6 MPa, and reaction time 8 h.

[0217] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 93.9% and the selectivity was 100%.

[0218] Test Example 19

[0219] The method of Test Example 1 was followed, except that the reaction conditions were: temperature 70° C., hydrogen pressure 6 MPa, and reaction time 8 h.

[0220] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 91.7% and the selectivity was 100%.

[0221] Test Example 20

[0222] The method of Test Example 1 was followed, except that the reaction conditions were: temperature 60° C., hydrogen pressure 6 MPa, and reaction time 8 h.

[0223] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 90.2% and the selectivity was 100%.

[0224] Test Example 21

[0225] The method of Test Example 1 was followed, except that the reaction conditions were: temperature 50° C., hydrogen pressure 6 MPa, and reaction time 8 h.

[0226] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 88.2% and the selectivity was 100%.

[0227] Test Example 22

[0228] Take 2L of 4wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 8g of supported catalyst A, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.2g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 6MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0229] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 95.3% and the selectivity was 100%.

[0230] Test Example 23

[0231] Take 2L of 4wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 8g of supported catalyst A, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.6g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 6MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0232] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 95.4% and the selectivity was 100%.

[0233] Test Example 24

[0234] Take 2L of 4wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 8g of supported catalyst A, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 2g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 6MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0235] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 95.3% and the selectivity was 100%.

[0236] Test Example 25

[0237] Take 2L of 4wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 12g of supported catalyst A, 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.6g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 6MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0238] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 98.9% and the selectivity was 100%.

[0239] Test Example 26

[0240] Take 2L of 4wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 8g of supported catalyst A, 0.08g of homogeneous catalyst triphenylphosphine rhodium chloride, and 0.32g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 95°C, hydrogen pressure 8MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0241] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 91.3% and the selectivity was 100%.

[0242] Test Example 27

[0243] Take 2L of 4wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 8g of supported catalyst A, 0.7g of homogeneous catalyst triphenylphosphine ruthenium chloride, and 1.5g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 6MPa, and reaction time 8h; hydrogenated nitrile rubber is obtained.

[0244] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 95.2% and the selectivity was 100%.

[0245] Test Example 28

[0246] The method of Test Example 1 was followed, except that supported catalyst A was replaced by supported catalyst O, to finally obtain hydrogenated nitrile rubber.

[0247] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 95.7% and the selectivity was 100%.

[0248] [Comparative Test Example 1]

[0249] The TiO2-SiO2 composite oxide support without surface treatment of Example 1 was used, and its infrared spectrum is shown in FIG3 , which is the infrared spectrum of the TiO2-SiO2 composite support without surface treatment.

[0250] Then, the active components were loaded according to the method of Example 12 to finally prepare a Cu / TiO2-SiO2 catalyst with a Cu content of 24 wt%. The particle size of the Cu atomic clusters was 20-50 nm.

[0251] According to the method of Test Example 1, hydrogenated nitrile rubber was finally obtained.

[0252] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 88.2% and the selectivity was 99%.

[0253] [Comparative Test Example 2]

[0254] Using the TiO2-SiO2 composite oxide support of Example 1, the method of Example 5 was followed, except that the copper nitrate solution was replaced with a nickel nitrate solution, to produce a Ni / ZrO2-SiO2 catalyst (supported catalyst DB1) with a Ni content of 24 wt%. The Ni atomic clusters had a particle size of 10 to 30 nm.

[0255] The method of Test Example 1 was followed, except that the supported catalyst A was replaced by the supported catalyst DB1, to finally obtain hydrogenated nitrile rubber.

[0256] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 78% and the selectivity was 82.5%.

[0257] [Comparative Test Example 3]

[0258] The method of Test Example 1 was followed, except that only supported catalyst A was used, as follows:

[0259] Take 2L of 3wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), add 9.4g of supported catalyst A, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0260] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 57.6% and the selectivity was 100%.

[0261] [Comparative Test Example 4]

[0262] The method of Test Example 5 was followed, except that only a homogeneous catalyst was used, as follows:

[0263] Take 2L of 3wt% NBR chlorobenzene solution (chlorobenzene is used to dissolve nitrile rubber), 0.4g of homogeneous catalyst triphenylphosphine rhodium chloride, and 1.0g of triphenylphosphine, and carry out catalyst hydrogenation reaction in a high-pressure reactor to obtain a rubber solution. The reaction conditions are: temperature 90°C, hydrogen pressure 8MPa, and reaction time 6h; hydrogenated nitrile rubber is obtained.

[0264] The hydrogenation degree and selectivity of the obtained hydrogenated nitrile rubber were tested according to the method of Test Example 1. The results showed that the hydrogenation degree was 67.2% and the selectivity was 100%.

[0265] [Comparative Test Example 5]

[0266] Take 85 g of SiO2 microsphere carrier (particle size: 20 μm, average pore size: 110 nm).

[0267] Take 5g of dimethyldioctadecylammonium chloride, add 95g of o-xylene, and mix evenly with 10mL of hydrochloric acid (mass fraction 37wt%) to prepare an impregnation solution. Use the above impregnation solution to impregnate the SiO2 microsphere carrier at 20°C, impregnate for 2h, and then dry at 60°C for 12h.

[0268] The infrared spectrum of the SiO2 carrier after surface treatment is shown in Figure 4.

[0269] As can be seen from Figures 1, 3 to 5, the surface of the composite oxide support is treated with an impregnation solution containing an organic cationic quaternary ammonium salt. The surface characteristics of the surface-treated composite oxide support are as follows: -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks at 610-720cm. The infrared spectrum of the TiO2-SiO2 composite oxide carrier without surface treatment and the infrared spectrum of the SiO2 carrier with surface treatment are at 610-720cm. -1 There are no three characteristic peaks at 2840-2970cm -1 The composite oxide support of the present invention can significantly improve the dispersion of active components on the catalyst surface and control the size of the active component atomic clusters to be no larger than 5 nm, thereby significantly improving the hydrogenation activity of the catalyst.

[0270] It can be seen from Test Examples 1-27 and Comparative Examples 1-4 that the present invention adopts a method of coordinating with a homogeneous catalyst to hydrogenate and saturate the high molecular polymer material at a relatively low temperature and pressure. The obtained hydrogenated nitrile rubber product has a high degree of hydrogenation and can also ensure the multiple use of the supported catalyst and the easy separation and recovery of the catalyst.

[0271] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, under the technical enlightenment provided by the present invention, as common knowledge in the art, other equivalent variations and improvements can be made, which should also be considered as the scope of protection of the present invention.

Claims

1. A composite oxide carrier, characterized in that include: SiO2 and Group IVB metal oxide, wherein the Group IVB metal oxide is TiO2 and / or ZrO2, and the surface characteristics of the composite oxide carrier are infrared spectrum at 610-720cm -1 There are three characteristic peaks at 2840-2970cm -1 There are three characteristic peaks.

2. The composite oxide support according to claim 1, characterized in that The surface characteristics of the composite oxide support are as follows: the infrared spectrum is 620±1cm -1 、649±1cm -1 、708±1cm -1 There is a characteristic peak at 2850±1cm; and / or, the surface characteristic of the composite oxide support is that the infrared spectrum is -1 、2919±1cm -1 、2955±1cm -1 There are characteristic peaks.

3. The composite oxide support according to claim 1, characterized in that The composite oxide carrier is obtained by surface treating a composite oxide carrier precursor of SiO2 and a Group IVB metal oxide with an impregnation solution containing an organic cationic quaternary ammonium salt. Preferably, the surface treatment is impregnation and drying. Preferably, the organic cationic quaternary ammonium salt is a C6 or higher long-chain alkyl quaternary ammonium salt, more preferably a C6 or higher long-chain alkyl halogen quaternary ammonium salt, more preferably selected from dimethyl dioctadecyl ammonium chloride, hexadecyl trimethyl ammonium chloride and C 12-14 -At least one of alkyl dimethyl ethyl benzyl ammonium chloride.

4. The composite oxide support according to any one of claims 1 to 3, characterized in that Based on the total weight of the composite oxide carrier, the content of the Group IVB metal oxide is 5 to 25 wt%, and the content of SiO2 is 75 to 95 wt%. Preferably, the content of the Group IVB metal oxide is 10 to 25 wt%, and the content of SiO2 is 75 to 90 wt%; and / or, the particle size of the composite oxide carrier is 5 to 30 μm; and / or, the average pore size is 100 to 1200 nm; and / or, the specific surface area is 30 to 200 m 2 / g.

5. A method for preparing a composite oxide support according to any one of claims 1 to 4, characterized in that: The following steps are involved: (1) first impregnating a SiO2 microsphere carrier with a solution containing a Group IVB metal compound, then first drying and first calcining to obtain a composite oxide carrier precursor, wherein the Group IVB metal compound is a titanium-containing compound and / or a zirconium-containing compound; (2) The composite oxide support precursor is surface treated with an impregnation solution containing an organic cationic quaternary ammonium salt to obtain the composite oxide support.

6. The preparation method according to claim 5, characterized in that: The impregnation solution containing organic cationic quaternary ammonium salt comprises organic cationic quaternary ammonium salt, solvent and acid; Preferably, in the impregnation solution containing the organic cationic quaternary ammonium salt, the concentration of the quaternary ammonium salt solution is 0.1-10 wt %.

7. The preparation method according to claim 6, characterized in that: The organic cationic quaternary ammonium salt is a C6 or higher long-chain alkyl quaternary ammonium salt, more preferably a C6 or higher long-chain alkyl halogen quaternary ammonium salt, more preferably selected from dimethyl dioctadecyl ammonium chloride, hexadecyl trimethyl ammonium chloride and C6 12-14 - at least one of alkyl dimethyl ethyl benzyl ammonium chloride; and / or The solvent is selected from at least one of deionized water, methanol, ethanol, acetone, butanone, tetrahydrofuran, o-xylene, p-xylene and pyridine, preferably selected from at least one of o-xylene, p-xylene and pyridine, more preferably o-xylene or pyridine; and / or The acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid and citric acid, preferably hydrochloric acid.

8. The preparation method according to any one of claims 5 to 7, characterized in that: The surface treatment is immersion and drying. Preferably, the immersion conditions include: temperature of 20-60° C., time of 0.5-8 h; the drying conditions include: temperature of 50-120° C., time of 2-10 h.

9. The preparation method according to any one of claims 5 to 8, characterized in that: The SiO2 microsphere carrier has a particle size of 5 to 30 μm; and / or an average pore size of 100 to 1200 nm; and / or a specific surface area of ​​30 to 200 m 2 / g.

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

11. The preparation method according to any one of claims 5 to 10, characterized in that: The molar ratio of the SiO2 microsphere carrier to the IVB group metal compound is 3 to 40:1; and / or, the first impregnation conditions include: a temperature of 20 to 60°C and a time of 0.5 to 8 hours; and / or, the first drying conditions include: a temperature of 105 to 130°C and a time of 2 to 8 hours; and / or, the first calcination conditions include: a temperature of 450 to 650°C and a time of 3 to 8 hours.

12. A supported catalyst comprising: The composite oxide carrier according to any one of claims 1 to 4, and the active component Cu and its oxide supported on the carrier; the atomic cluster particle size of the active component copper is not greater than 5 nm; the content of Cu and its oxide calculated as CuO is 5 to 25 wt% based on the total weight of the supported catalyst.

13. The supported catalyst according to claim 12, characterized in that The supported catalyst has a particle size of 5 to 30 μm; and / or an average pore size of 100 to 1200 nm; and / or a specific surface area of ​​30 to 200 m 2 / g; and / or, the atomic cluster particle size of the active component copper is 2 to 5 nm.

14. A method for preparing a supported catalyst according to claim 12 or 13, comprising the following steps: The composite oxide support according to any one of claims 1 to 4 or the composite oxide support obtained by the preparation method according to any one of claims 5 to 9 is secondly impregnated with a solution of a soluble salt of Cu, and then second dried and second calcined.

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

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

17. A catalyst composition comprising a homogeneous catalyst and the supported catalyst according to claim 12 or 13.

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

1.

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

3.

20. A method for hydrogenating a high molecular weight polymer, comprising: An organic solvent is used to dissolve the high molecular polymer, and then the catalyst composition according to any one of claims 17 to 19 is added to react the high molecular polymer with hydrogen in the presence of the catalyst composition.

21. The hydrogenation method according to claim 20, characterized in that The amount of the supported catalyst is 5-20 wt% of the polymer.

22. The hydrogenation method according to claim 20, characterized in that The reaction conditions include: temperature of 30-90° C., hydrogen pressure of 5-10 MPa, and reaction time of 5-10 h.

23. The hydrogenation method according to any one of claims 20 to 22, characterized in that: The high molecular polymer is nitrile rubber.

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

25. The hydrogenated high molecular polymer obtained by the hydrogenation method according to any one of claims 20 to 24, preferably, the hydrogenated high molecular polymer is hydrogenated nitrile rubber.

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