Petroleum resin hydrogenation catalyst, its preparation method and application

Abstract

The application discloses a petroleum resin hydrogenation catalyst and a preparation method thereof. The petroleum resin hydrogenation catalyst comprises a first phase and a second phase; the first phase comprises aluminum oxide and nickel oxide, the second phase comprises aluminum oxide, zinc oxide and nickel oxide, and the catalyst has a spherical core-shell structure. The preparation method of the petroleum resin hydrogenation catalyst comprises the following steps: firstly, preparing an aluminum oxide-nickel oxide composite material; then, uniformly dispersing the composite material with a surfactant and a hydrocarbon-containing compound to obtain material A; uniformly mixing aluminum sol, a zinc-containing compound, a nickel-containing compound, a curing agent and an emulsifier additive to obtain a mixed solution; finally, mixing the material A with the mixed solution, and further performing forming, aging, extraction, washing, drying and calcination to obtain the petroleum resin hydrogenation catalyst. The petroleum resin hydrogenation catalyst has the advantages of high sulfur resistance, high hydrogenation decolorization performance and high stability, and is especially suitable for C5 and C9 petroleum resin hydrogenation treatment processes.

Description

Technical Field

[0001] This invention belongs to the field of petrochemical technology and relates to a catalytic material and its preparation, particularly to the preparation and application of a petroleum resin hydrogenation catalyst. Background Technology

[0002] Petroleum resin is a functional resin with a relatively low molecular weight, possessing tackifying, adhesive, and compatibility properties with other resins. It is mainly used in coatings, adhesives, printing inks, rubber additives, and paper additives. Petroleum resins generally have a dark color and poor thermal and oxidative stability. In particular, the presence of unsaturated double bonds and aromatic compounds affects the resin's color, stability, and compatibility with other resins, limiting its application range. Petroleum resins can be modified to expand their application range, with hydrogenation being an effective method. Hydrogenation refining saturates the unsaturated bonds in the resin molecules through catalytic hydrogenation, thereby improving its color, thermal stability, and oxidative stability.

[0003] Catalysts for the hydrogenation of petroleum resins mainly include noble metal catalysts and non-noble metal catalysts. Noble metal catalysts are primarily platinum and palladium catalysts, which can effectively limit side reactions during resin hydrogenation and cracking. Non-noble metal catalysts are mainly nickel-based catalysts, which can cause slight degradation of the resin during hydrogenation, while appropriate hydrogenation and cracking can improve the resin's miscibility.

[0004] In the hydrogenation reaction of petroleum resins, both noble metal and non-noble metal catalysts exhibit high olefin hydrogenation activity. However, these metals, especially Pt or Pd, are highly sensitive to sulfides in the feedstock and are easily poisoned and deactivated. Generally, a protective catalyst is added before the main catalyst, and this problem is addressed through catalyst gradation.

[0005] CN201811261920.3 discloses a method for preparing a C5 petroleum resin hydrogenation catalyst. This method uses aluminum isopropoxide and isopropanol solution as the reaction substrate, zirconium and magnesium as additives, nickel as the catalytically active component, and an organic surfactant as a dispersant to prepare a nickel-based C5 petroleum resin hydrogenation catalyst. In this nickel-based C5 petroleum resin hydrogenation catalyst, the main active component nickel accounts for 40 wt%-60 wt% of the catalyst mass, zirconium and magnesium additives account for 1 wt%-15 wt% of the catalyst mass, the organic nonionic surfactant accounts for 0.1 wt%-10 wt% of the catalyst mass, and the balance is silica and alumina. This patent reduces the acidity of the support by adding additives, but does not improve the sulfur resistance of the catalyst, and still requires matching refined catalysts to protect the main catalyst.

[0006] CN202010460651.4 discloses a method for hydrogenating high-sulfur petroleum resin, belonging to the field of polymer hydrogenation technology. It uses a supported bimetallic alloy catalyst as a pre-hydrogenation desulfurization catalyst and a supported metal catalyst as a hydrogenation decolorization catalyst. A two-stage fixed-bed continuous hydrogenation method is employed to hydrogenate the resin, resulting in a hydrogenated resin with improved color (water-white) and good thermal stability. However, this patent also uses catalyst gradation to achieve hydrogenation of high-sulfur resin, and the use of a bimetallic alloy as the desulfurization catalyst is not conducive to widespread application. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a petroleum resin hydrogenation catalyst, its preparation method, and its application, particularly a petroleum resin hydrogenation catalyst with high sulfur resistance and high stability, along with its preparation method and application. The petroleum resin hydrogenation catalyst provided by this invention has a spherical core-shell structure. Through optimization of the pore structure and acidity, it achieves dual functions of shell-layer hydrogenation desulfurization and core-layer hydrogenation decolorization on a single catalyst. The petroleum resin hydrogenation catalyst provided by this invention has the advantages of strong sulfur resistance, high hydrogenation decolorization performance, and high stability, making it particularly suitable for the hydrogenation treatment of C5 and C9 petroleum resins.

[0008] The first aspect of the present invention provides a petroleum resin hydrogenation catalyst, the petroleum resin hydrogenation catalyst comprising a first phase and a second phase; wherein the first phase comprises alumina and nickel oxide, and the second phase comprises alumina, zinc oxide and nickel oxide; the catalyst has a spherical core-shell structure, with the first phase as the core layer and the second phase as the shell layer.

[0009] Furthermore, in the above-mentioned petroleum resin hydrogenation catalyst, based on the weight of the catalyst, the nickel oxide content is 20wt% to 50wt%, the zinc oxide content is 10wt% to 30wt%, and the aluminum oxide content is 20wt% to 70wt%; wherein, the weight ratio of nickel oxide in the core layer to nickel oxide in the shell layer is 3:1 to 10:1, preferably 3:1 to 7:1.

[0010] Furthermore, in the above-mentioned petroleum resin hydrogenation catalyst, the specific surface area of ​​the catalyst is 180–250 m². 2 / g, with a pore volume of 0.50~0.80mL / g.

[0011] Furthermore, in the above-mentioned petroleum resin hydrogenation catalyst, the particle diameter of the catalyst is 0.4 to 2.0 mm, preferably 0.5 to 1.8 mm.

[0012] Furthermore, in the above-mentioned petroleum resin hydrogenation catalyst, the shell thickness of the catalyst is 0.3 to 0.6 times the diameter of the catalyst particles.

[0013] Furthermore, in the above-mentioned petroleum resin hydrogenation catalyst, the catalyst attrition index is not greater than 0.05%.

[0014] Furthermore, in the above-mentioned petroleum resin hydrogenation catalyst, the side pressure strength of the catalyst is greater than 20 N / mm.

[0015] A second aspect of the present invention provides a method for preparing a petroleum resin hydrogenation catalyst, comprising the following steps: (1) Preparation of alumina-nickel oxide composite material; (2) Under contact conditions, the alumina-nickel oxide composite material, surfactant, and hydrocarbon compound obtained in step (1) are thoroughly mixed and dispersed to obtain material A; (3) Under contact conditions, aluminum sol, zinc-containing compound, nickel-containing compound, curing agent, emulsifier and additives are thoroughly mixed to obtain a mixed solution; (4) Under contact conditions, the material A obtained in step (2) is fully mixed with the mixed solution obtained in step (3) to obtain an oil-in-water emulsion, which is further processed by molding, aging, extraction, washing, drying and calcination to obtain a petroleum resin hydrogenation catalyst.

[0016] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the specific process for preparing the alumina-nickel oxide composite material in step (1) is as follows: Alumina powder is thoroughly mixed with a nickel-containing compound solution, and after uniform mixing, it is dried and calcined to obtain the nickel oxide-alumina composite material. The nickel-containing compound is a nickel salt, preferably a soluble nickel salt. Specifically, the nickel-containing compound can be one or more of nickel nitrate, nickel sulfate, nickel chloride, and nickel acetate. The drying conditions are as follows: drying temperature is 100℃~150℃, and drying time is 2~8h; the calcination conditions are as follows: calcination temperature is 450℃~600℃, preferably 480℃~550℃, and calcination time is 2~8h. The specific surface area of ​​alumina is 200~330m². 2 / g, pore volume not less than 0.90mL / g; the alumina powder is preferably obtained by high-temperature calcination of boehmite, usually at a calcination temperature of 650℃~950℃, preferably 750℃~950℃.

[0017] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, after the alumina-nickel oxide composite material is prepared, it is preferable to further pulverize it. After pulverization, the particle size of the sample is controlled to be 2-10 micrometers, preferably 3-8 micrometers. Specifically, the pulverization can be carried out on a ball mill.

[0018] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the hydrophilic-lipophilic balance (HLB) value of the surfactant in step (2) is 16-18, specifically at least one of Tween 20, Pinto-PineO-25, and Pinto-PineO-30. The amount of surfactant added is 5.0wt% to 15.0wt% of the weight of the alumina-nickel oxide composite material.

[0019] In the above method for preparing petroleum resin hydrogenation catalyst, the hydrocarbon-containing compound in step (2) has a kinematic viscosity of 20-40 mm at 40°C. 2 / s, preferably 25-35mm 2 / s. More specifically, the hydrocarbon-containing compound may be selected from at least one of white oil, diesel oil, kerosene, lubricating oil, C10-C15 alkane compounds, etc.; preferably white oil and / or diesel oil; further, the amount of the hydrocarbon-containing compound added is 1.0 to 3.5 times the weight of the alumina-nickel oxide composite material, preferably 1.5 to 3.0 times.

[0020] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the dispersion in step (2) is carried out under ultrasonic conditions, and the frequency of the ultrasonic waves is 25KHZ to 130KHZ.

[0021] In the above method for preparing petroleum resin hydrogenation catalyst, the solid content of material A obtained in step (2) is 25wt% to 40wt%.

[0022] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the zinc-containing compound in step (3) is a zinc-soluble salt, and the specific zinc-containing compound can be one or more of zinc nitrate, zinc sulfate, and zinc chloride.

[0023] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the nickel-containing compound in step (3) is a soluble nickel salt of nickel. Specifically, the nickel-containing compound can be one or more of nickel nitrate, nickel sulfate, nickel chloride, and nickel acetate.

[0024] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the Al2O3 content in the aluminum sol in step (3) is 20wt% to 45wt%, preferably 25wt% to 40wt%. The aluminum sol can be prepared by existing methods, such as reacting aluminum with hydrochloric acid solution, reacting aluminum with aluminum chloride solution, or reacting boehmite prepared by the aluminum alkoxide method with nitric acid solution.

[0025] In the above method for preparing petroleum resin hydrogenation catalyst, the curing agent in step (3) is one or more of hexamethylenetetramine and urea, preferably hexamethylenetetramine; the mass concentration of the curing agent is 30wt% to 70wt%; the amount of the curing agent added is 5wt% to 35wt% of the weight of alumina in the aluminum sol, preferably 10wt% to 30wt%.

[0026] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the emulsifier in step (3) is a nonionic emulsifier with a hydrophilic-lipophilic balance (HLB) value of 10 to 15.8. The emulsifier is at least one of polyoxyethylene sorbitan fatty acid ester, fatty alcohol polyoxyethylene ether, etc. Specifically, the emulsifier can be selected from at least one of Tween 40, Tween 60, Tween 65, Tween 80, AEO-7, AEO-9, and AEO-15.

[0027] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the mass concentration of the emulsifier in step (3) is 0.5wt% to 2.5wt%, and the amount of emulsifier added is 0.5wt% to 5.0wt% of the alumina in the aluminum sol, preferably 0.5wt% to 4.5wt%.

[0028] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the auxiliary agent mentioned in step (3) is selected from one or more of methacryloyloxyethyltrimethylammonium chloride (DMC), dimethyl diallyl ammonium chloride (DMDAAC), acryloyloxyethyltrimethylammonium chloride (DAC), and polyacrylamide, preferably polyacrylamide; the concentration of the auxiliary agent is 1wt% to 5wt%, and the amount of the auxiliary agent added is 1wt% to 15wt% of the alumina in the aluminum sol.

[0029] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the mixing in step (4) can be carried out under high-speed shear conditions, and the rotation speed can generally be 10,000 to 25,000 rpm.

[0030] In the above method for preparing petroleum resin hydrogenation catalyst, the solid content of the oil-in-water emulsion in step (4) is 5wt% to 10wt%.

[0031] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the molding in step (4) is carried out by oil column molding, in which the water-in-oil emulsion in step (4) is dripped into the oil column. The oil phase medium used in the oil injection molding process is either white oil or diesel oil, preferably white oil. The molding temperature is 90℃~110℃, preferably 95℃~105℃.

[0032] In the above method for preparing petroleum resin hydrogenation catalyst, the aging process in step (4) has a temperature of 130℃~180℃, a pressure of 0.2~0.5MPa, and an aging time of 2~6h.

[0033] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the washing in step (4) includes two steps: organic solvent washing and water washing. The organic solvent used for organic solvent washing is selected from at least one of petroleum ether, cyclohexane, toluene, and anhydrous ethanol, preferably a mixed solution of at least one of petroleum ether, cyclohexane, and toluene with anhydrous ethanol. Furthermore, the volume ratio of anhydrous ethanol in the mixed solution is 25% to 50%. The temperature of the water washing process is 70°C to 90°C.

[0034] In the above-mentioned method for preparing petroleum resin hydrogenation catalyst, the drying temperature in step (4) is 100℃~150℃ and the drying time is 6~10 hours; the calcination temperature is 450℃~600℃ and the calcination time is 2~6 hours.

[0035] A third aspect of the present invention provides the application of the above-mentioned petroleum resin hydrogenation catalyst in the petroleum resin hydrogenation process.

[0036] In the above applications, the petroleum resin can be C5 and / or C9 resin, the color of the petroleum resin is not greater than 12 (Cyber), the softening point is not less than 110, the S content is not less than 200 μg / g, and the resin is generally dissolved in a solvent and then subjected to hydrogenation reaction.

[0037] In the above applications, the operating conditions for the hydrotreating process are: reaction pressure of 10–20 MPa, reaction temperature of 240°C–310°C, and liquid hourly space velocity of 0.3–2.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100–1000.

[0038] In the above applications, the hydrotreating process is preferably carried out in a fixed-bed hydrotreating reactor.

[0039] In the above applications, the petroleum resin hydrogenation catalyst needs to be reduced before use. The reduction pressure is 10-20 MPa, the reduction temperature is 400℃-600℃, and the reduction time is 8-15 h.

[0040] The petroleum resin hydrogenation catalyst and its preparation method provided by this invention have the following excellent technical effects: 1. The petroleum resin hydrogenation catalyst provided by this invention has a core-shell structure, with alumina-nickel oxide as the core and alumina-zinc oxide-nickel oxide as the shell. This achieves the goal of first hydrogenating and adsorbing desulfurization of the raw material on a single catalyst, followed by hydrogenating and decolorizing, and significantly improves the catalyst's hydrogenation activity and stability. In preparing the core, macroporous alumina with high water absorption is used, enhancing the bonding between the nickel and alumina during impregnation. Furthermore, the moderately large pore size is beneficial for the hydrogenation of macromolecules in the resin.

[0041] 2. In the method for preparing petroleum resin hydrogenation catalyst provided by the present invention, an oil-in-water emulsion is prepared by alumina-nickel oxide composite material, zinc-containing compound, nickel-containing compound, and aluminum sol. Then, it is formed by oil injection molding. During droplet forming, the emulsion droplets enter the oil phase medium and shrink into spherical droplets with a water film on the outer surface and an emulsion inside under the action of surface tension. Due to the changes in temperature and pH value, the stability of the emulsion is destroyed. The alumina-nickel oxide composite material is in a free state in the zinc and nickel-aluminum sol solution. Under the action of high molecular weight amine compound additives, physical and chemical changes occur. Through adsorption, bridging, cross-linking, and neutralization of the charge on the surface of suspended matter, the particles change from repulsion to attraction. Then, the alumina-nickel oxide composite material aggregates and integrates into a core structure. At the same time, the curing agent in the emulsion decomposes under heat, and the released alkaline gas causes the aluminum sol encapsulating the core structure to form gel spheres, thereby forming a core-shell structured spherical resin hydrogenation catalyst.

[0042] 3. In the method for preparing petroleum resin hydrogenation catalyst provided by the present invention, the wettability and dispersibility of alumina-nickel oxide composite material can be improved by using additives and combining ultrasonic dispersion, ensuring that it can be uniformly dispersed in aluminum sol and ensuring the stability of the dispersion system. This solves the problem that alumina-nickel oxide composite material has high surface energy and poor dispersion, making it impossible to prepare core-shell structure catalysts.

[0043] 4. In the method for preparing petroleum resin hydrogenation catalyst provided by the present invention, a high-temperature and high-pressure aging process is used to obtain a shell with a larger pore size. At the same time, the organic matter in the aging spheres can be recovered by extraction, which prevents environmental pollution and avoids the problem of decomposition of organic matter in the spheres during the calcination process, resulting in a decrease in strength. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of the SEM line scan of the sample prepared in Embodiment A1 of the present invention.

[0045] Figure 2 The NiO content distribution diagrams are for the samples prepared in Example 1, Comparative Example 1, and Comparative Example 2. Detailed Implementation

[0046] The specific embodiments of the present invention will be described in detail below with reference to specific examples, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments.

[0047] Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "comprises" shall be understood to include the stated elements or components without excluding other elements or other components.

[0048] Unless otherwise specified, the experimental methods used in the following examples and comparative examples are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following examples were purchased from conventional biochemical reagent stores.

[0049] The analytical methods of this invention are as follows: Specific surface area and pore volume were measured using the cryogenic liquid nitrogen physical adsorption method, with the instrument being an ASAP2405 or 2420 physical adsorption instrument manufactured by a US company; external acid content was measured using pyridine adsorption infrared spectroscopy, with a NICOLET 6700 Fourier transform infrared spectrometer; wear index was measured using the drum method, with a KM-ZV wear meter; metal composition was measured using inorganic spectrophotometry. Lateral compressive strength was measured using a ZQJ-II intelligent particle strength testing machine. Metal distribution was measured using SEM.

[0050] Example 1 The pseudoboehmite prepared by the carbonization method was calcined at 850℃ for 3 hours to obtain a specific surface area of ​​203 m². 2 / g, pore volume 0.90mL / g alumina. Weigh 30g alumina, impregnate it with a nickel nitrate solution with a NiO content of 18wt%, dry at 120℃ for 6h, calcine at 500℃ for 5h, and repeat the impregnation process multiple times to prepare an alumina-nickel oxide composite material with a NiO content of 65wt%.

[0051] Weigh 40g of the above alumina-nickel oxide composite material and grind it into powder with a particle size ≤5.0 micrometers using a ball mill. Add 4.8g of O-25 to a solution with a kinematic viscosity of 33mm at 40℃. 2 In 100g of white oil per second, after stirring evenly, the above-ground powder was added, and then stirred under 100KHZ ultrasonication to obtain a uniformly dispersed system with a solid content of 27.62wt%. Weigh 150g of aluminum sol with an Al2O3 content of 30wt%, then add 49.63g of zinc chloride and 17.36g of nickel chloride hexahydrate and stir until completely dissolved. Next, add 15.8g of a 36wt% hexamethylenetetramine solution, 85g of a 1.0wt% Tween 80 emulsifier, and 190g of a 1.5wt% polyacrylamide, and stir until homogeneous to obtain an aluminum sol mixture. The above dispersion system was added to the aluminum sol mixture and mixed under a high shear device at a speed of 18,000 rpm to obtain an oil-in-water emulsion with a solid content of 6.1 wt%. The viscosity at 40°C is 35 mm. 2 The above-mentioned oil-in-water (O / W) emulsion was added dropwise to white oil at 95℃ to form the gel spheres. After forming, the gel spheres were aged at 150℃ for 2 hours. After aging, the gel spheres were first washed with a 1:1 volume ratio of petroleum ether and anhydrous ethanol to remove the medium oil from the formed material, then washed with deionized water at 85℃, dried at 130℃ for 8 hours, and calcined at 600℃ for 3 hours to obtain spherical catalyst A-1. Its properties are shown in Table 1.

[0052] Example 2 The process is basically the same as in Example 1, except that the surfactant Pingpingjia O-25 is replaced with Tween 20, and the aging time of the gel microspheres after molding is changed from 2 hours at 150°C to 4 hours at 135°C, thus obtaining spherical catalyst A2, the properties of which are shown in Table 1.

[0053] Example 3 The process is basically the same as in Example 1, except that the polyacrylamide is replaced with methacryloyloxyethyltrimethylammonium chloride to prepare spherical catalyst A2, the properties of which are shown in Table 1.

[0054] Example 4 The method is basically the same as in Example 1, except as follows: the pseudoboehmite prepared by the aluminum sulfate method was calcined at 800°C for 3.5 h to obtain a specific surface area of ​​213 m². 2 Alumina-nickel oxide composite material with a NiO content of 50wt% was prepared by repeatedly impregnating alumina with a pore volume of 1.050mL / g and a pore volume of 1.050mL / g. The emulsifier was replaced with AEO-9 to obtain spherical catalyst A3, the properties of which are shown in Table 1.

[0055] Example 5 The pseudoboehmite prepared by the carbonization method was calcined at 850℃ for 3 hours to obtain a specific surface area of ​​203 m². 2 / g, pore volume 0.90mL / g alumina. Weigh 30g alumina, impregnate it with a nickel nitrate solution with a NiO content of 18wt%, dry at 140℃ for 4h, calcine at 450℃ for 6h, and repeat the impregnation process multiple times to prepare an alumina-nickel oxide composite material with a NiO content of 55wt%.

[0056] Weigh 40g of the above alumina-nickel oxide composite material and grind it into powder with a particle size ≤5.0 micrometers using a ball mill. Add 4.0g of Pingpingjia O-30 to a solution with a kinematic viscosity of 30mm at 40℃. 2The powder was added to 85g of white oil per s after stirring evenly, and then stirred under 120KHZ ultrasonication to obtain a uniform dispersion system with a solid content of 31.0wt%. Weigh 130g of aluminum sol with an Al2O3 content of 35wt%, then add 38.3g of zinc chloride and 15.6g of nickel chloride hexahydrate and stir until completely dissolved. Next, add 11.5g of a 45wt% hexamethylenetetramine solution, 165g of an emulsifier with an HLB value of 10.5 and a concentration of 0.70wt% (Tween 65), and 220g of a 1.2wt% acryloyloxyethyltrimethylammonium chloride. Stir and mix thoroughly to obtain an aluminum sol mixture. The above dispersion system was added to the aluminum sol mixture and mixed under a high shear device at a speed of 23,000 rpm to obtain an oil-in-water emulsion with a solid content of 5.64 wt%. The viscosity at 40°C is 30 mm. 2 The above-mentioned oil-in-water (O / W) emulsion was added dropwise to white oil at 100℃ to form the gel microspheres. After forming, the gel microspheres were aged at 170℃ for 2 hours. After aging, the gel microspheres were first washed with a mixed solution of petroleum ether and anhydrous ethanol at a volume ratio of 1:0.5 to remove the medium oil from the formed material, then washed with deionized water at 75℃, and then dried at 120℃ for 8 hours. After calcination at 550℃ for 3 hours, spherical catalyst A5 was obtained, and its properties are shown in Table 1.

[0057] Comparative Example 1 The pseudoboehmite prepared by the carbonization method was calcined at 850℃ for 3 hours to obtain a specific surface area of ​​203 m². 2 / g, pore volume 0.90mL / g alumina. Weigh 30g alumina, impregnate it with a nickel nitrate solution with a NiO content of 18wt%, dry at 120℃ for 6h, calcine at 500℃ for 5h, and repeat the impregnation process multiple times to prepare an alumina-nickel oxide composite material with a NiO content of 65wt%.

[0058] Weigh 40g of the above alumina-nickel oxide composite material and grind it into powder with a particle size ≤5.0 micrometers using a ball mill. Add 4.8g of O-25 to a solution with a kinematic viscosity of 33mm at 40℃. 2 In 100g of white oil per second, after stirring evenly, the above-ground powder was added, and then stirred under 100KHZ ultrasonication to obtain a uniformly dispersed system with a solid content of 27.62wt%. Weigh 150g of aluminum sol with an Al2O3 content of 30wt%, then add 49.63g of zinc chloride and 17.36g of nickel chloride and stir until completely dissolved. Then add 15.8g of hexamethylenetetramine solution with a concentration of 36wt%, 85g of deionized water, and 190g of polyacrylamide with a concentration of 1.5wt%, and stir to mix evenly to obtain an aluminum sol mixture. The above dispersion system was added to the aluminum sol mixture and mixed under a high shear device at a speed of 18,000 rpm to obtain an oil-in-water emulsion with a solid content of 6.1 wt%. The viscosity at 40°C is 35 mm. 2 The above-mentioned oil-in-water (O / W) emulsion was added dropwise to white oil at 95℃ to form the gel spheres. After forming, the gel spheres were aged at 150℃ for 2 hours. After aging, the gel spheres were first washed with a 1:1 volume ratio of petroleum ether and anhydrous ethanol to remove the medium oil from the formed material, then washed with deionized water at 85℃, dried at 130℃ for 8 hours, and calcined at 600℃ for 3 hours to obtain spherical catalyst F1. Its properties are shown in Table 1.

[0059] Comparative Example 2 The pseudoboehmite prepared by the carbonization method was placed in a crucible and calcined at 850℃ for 3 hours to obtain a specific surface area of ​​203 m². 2 / g, pore volume 0.90mL / g alumina. Weigh 30g alumina, impregnate it with a nickel nitrate solution with a NiO content of 18wt%, dry at 120℃ for 6h, calcine at 500℃ for 5h, and repeat the impregnation process multiple times to prepare an alumina-nickel oxide composite material with a NiO content of 65wt%.

[0060] Weigh 40g of the above alumina-nickel oxide composite material and grind it into powder with a particle size ≤5.0 micrometers using a ball mill. Add 4.8g of O-25 to a solution with a kinematic viscosity of 33mm at 40℃. 2 In 100g of white oil per second, after stirring evenly, the above-ground powder was added, and then stirred under 100KHZ ultrasonication to obtain a uniformly dispersed system with a solid content of 27.62wt%. Weigh 150g of aluminum sol with an Al2O3 content of 30wt%, then add 49.63g of zinc chloride and 17.36g of nickel chloride and stir until completely dissolved. Then add 15.8g of a 36wt% hexamethylenetetramine solution, 85g of an HLB value of 15 emulsifier Tween 80 with a concentration of 1.0wt%, and 190g of deionized water, and stir to mix evenly to obtain an aluminum sol mixture. The above dispersion system was added to the aluminum sol mixture and mixed under a high shear device at a speed of 18,000 rpm to obtain an oil-in-water emulsion with a solid content of 6.1 wt%. The viscosity at 40°C is 35 mm. 2The above-mentioned oil-in-water (O / W) emulsion was added dropwise to white oil at 95℃ to form the gel microspheres. After forming, the gel microspheres were aged at 150℃ for 2 hours. After aging, the gel microspheres were first washed with a 1:1 volume ratio of petroleum ether and anhydrous ethanol to remove the medium oil from the formed material, then washed with deionized water at 85℃, dried at 130℃ for 8 hours, and calcined at 600℃ for 3 hours to obtain spherical catalyst F2. Its properties are shown in Table 1.

[0061] Table 1 Properties of the prepared catalyst The catalyst was loaded into a 100 mL small evaluation device. Before evaluation, the catalyst was reduced under the following conditions: pressure 15 MPa, temperature 500 °C, and reduction time 8 h. Before evaluation, the solid petroleum resin was dissolved and diluted with cyclohexane. The properties of the petroleum resin before and after dissolution and dilution are shown in Table 2. The evaluation conditions are shown in Table 3. After evaluation, the product was separated under reduced pressure. The properties of the hydrogenated petroleum resin after 1000 hours of evaluation are shown in Table 4.

[0062] Table 2 Properties of Petroleum Resins Table 3 Evaluation process conditions for petroleum resins Table 4. Catalyst evaluation results after 1000 hours The generated oils from A1, F1, and F2 after 2000 hours of operation were analyzed. The activity of the comparative example F1 was set at 100. The evaluation results of the other oils compared with the activity of the comparative example F1 are shown in Table 5.

[0063] Table 5. Catalyst evaluation results after 2000 hours The data in the table show that the catalyst prepared in this invention has good sulfur resistance and decolorization performance after 1000h and 2000h of operation, and the catalyst activity stability is good.

Claims

1. A petroleum resin hydrogenation catalyst, wherein the petroleum resin hydrogenation catalyst comprises a first phase and a second phase; wherein, The first phase comprises alumina and nickel oxide, and the second phase comprises alumina, zinc oxide, and nickel oxide. The catalyst has a spherical core-shell structure, with the first phase as the core and the second phase as the shell. Based on the weight of the catalyst, the nickel oxide content is 20wt%–50wt%, the zinc oxide content is 10wt%–30wt%, and the alumina content is 20wt%–70wt%. The weight ratio of nickel oxide in the core to nickel oxide in the shell is 3:1 to 10:

1.

2. The petroleum resin hydrogenation catalyst according to claim 1, characterized in that: The weight ratio of nickel oxide in the core layer to nickel oxide in the shell layer is 3:1 to 7:

1.

3. The petroleum resin hydrogenation catalyst according to claim 1, characterized in that: The specific surface area of ​​the catalyst is 180–250 m². 2 / g, with a pore volume of 0.50~0.80mL / g.

4. The petroleum resin hydrogenation catalyst according to claim 1, characterized in that: The catalyst particles have a diameter of 0.4–2.0 mm.

5. The petroleum resin hydrogenation catalyst according to claim 1, characterized in that: The catalyst particles have a diameter of 0.5–1.8 mm.

6. The petroleum resin hydrogenation catalyst according to claim 1, characterized in that: The thickness of the catalyst shell is 0.3 to 0.6 times the diameter of the catalyst particles.

7. The petroleum resin hydrogenation catalyst according to claim 1, characterized in that: The catalyst attrition index is no greater than 0.05%.

8. The petroleum resin hydrogenation catalyst according to claim 1, characterized in that: The catalyst has a lateral compressive strength greater than 20 N / mm.

9. A method for preparing the petroleum resin hydrogenation catalyst according to any one of claims 1-8, comprising the following steps: (1) Preparation of alumina-nickel oxide composite material; (2) Under contact conditions, the alumina-nickel oxide composite material, surfactant, and hydrocarbon compound obtained in step (1) are thoroughly mixed and dispersed to obtain material A; (3) Under contact conditions, aluminum sol, zinc-containing compound, nickel-containing compound, curing agent, emulsifier and additive are thoroughly mixed to obtain a mixed solution. The additive is selected from one or more of methacryloyloxyethyltrimethylammonium chloride, dimethyl diallyl ammonium chloride, acryloyloxyethyltrimethylammonium chloride and polyacrylamide. (4) Under contact conditions, the material A obtained in step (2) is fully mixed with the mixed solution obtained in step (3) to obtain an oil-in-water emulsion, which is further processed by molding, aging, extraction, washing, drying and calcination to obtain a petroleum resin hydrogenation catalyst.

10. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The process of preparing alumina-nickel oxide composite material in step (1) is as follows: alumina powder is thoroughly mixed with a nickel-containing compound solution, and after uniform mixing, it is dried and calcined to obtain nickel oxide-alumina composite material, wherein the nickel-containing compound is a nickel salt.

11. The method for preparing the petroleum resin hydrogenation catalyst according to claim 10, characterized in that: Nickel-containing compounds are soluble nickel salts.

12. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9 or 10, characterized in that: The nickel-containing compound is one or more of nickel nitrate, nickel sulfate, nickel chloride, and nickel acetate.

13. The method for preparing the petroleum resin hydrogenation catalyst according to claim 10, characterized in that: The drying process conditions are as follows: drying temperature is 100℃~150℃, drying time is 2~8h; the calcination process conditions are as follows: calcination temperature is 450℃~600℃, calcination time is 2~8h.

14. The method for preparing the petroleum resin hydrogenation catalyst according to claim 13, characterized in that: The roasting temperature is 480℃~550℃.

15. The method for preparing the petroleum resin hydrogenation catalyst according to claim 10, characterized in that: The specific surface area of ​​alumina is 200–330 m². 2 / g, pore volume not less than 0.90mL / g.

16. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: After the alumina-nickel oxide composite material is prepared, it is further pulverized to control the particle size of the sample to be 2-10 micrometers.

17. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: After the alumina-nickel oxide composite material is prepared, it is further pulverized to control the particle size of the sample to be 3-8 micrometers.

18. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The hydrophilic-lipophilic balance value of the surfactant in step (2) is 16 to 18, and the surfactant is at least one of Tween 20, Pinto-PineO-25, and Pinto-PineO-30; the amount of surfactant added is 5.0 wt% to 15.0 wt% of the weight of the alumina-nickel oxide composite material.

19. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The kinematic viscosity of the hydrocarbon compound in step (2) at 40°C is 20–40 mm. 2 / s, the hydrocarbon compound is selected from at least one of white oil, diesel oil, kerosene, lubricating oil, and C10-C15 alkane compounds; the amount of hydrocarbon compound added is 1.0 to 3.5 times the weight of the alumina-nickel oxide composite material.

20. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The kinematic viscosity of the hydrocarbon compound in step (2) at 40°C is 25–35 mm. 2 / s; the hydrocarbon compound is white oil and / or diesel oil; the amount of hydrocarbon compound added is 1.5 to 3.0 times the weight of the alumina-nickel oxide composite material.

21. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The zinc-containing compound in step (3) is a soluble salt of zinc.

22. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9 or 21, characterized in that: The zinc-containing compound in step (3) is one or more of zinc nitrate, zinc sulfate, and zinc chloride.

23. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The nickel-containing compound in step (3) is a nickel-soluble nickel salt.

24. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9 or 23, characterized in that: The nickel-containing compound in step (3) is one or more of nickel nitrate, nickel sulfate, nickel chloride, and nickel acetate.

25. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The Al2O3 content in the aluminum sol in step (3) is 20wt% to 45wt%.

26. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The Al2O3 content in the aluminum sol in step (3) is 25wt% to 40wt%.

27. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The curing agent in step (3) is one or more of hexamethylenetetramine and urea; the mass concentration of the curing agent is 30wt% to 70wt%; the amount of curing agent added is 5wt% to 35wt% of the weight of alumina in the aluminum sol.

28. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The curing agent in step (3) is hexamethylenetetramine; the mass concentration of the curing agent is 30wt% to 70wt%; the amount of curing agent added is 10wt% to 30wt% of the weight of alumina in the aluminum sol.

29. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The emulsifier in step (3) is a nonionic emulsifier with a hydrophilic-lipophilic balance value of 10 to 15.

8.

30. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The emulsifier in step (3) is at least one of polyoxyethylene sorbitan fatty acid ester and fatty alcohol polyoxyethylene ether.

31. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9 or 30, characterized in that: The emulsifier in step (3) is at least one of Tween 40, Tween 60, Tween 65, Tween 80, AEO-7, AEO-9, and AEO-15.

32. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The mass concentration of the emulsifier in step (3) is 0.5wt% to 2.5wt%, and the amount of emulsifier added is 0.5wt% to 5.0wt% of the alumina in the aluminum sol.

33. The method for preparing the petroleum resin hydrogenation catalyst according to claim 32, characterized in that: The amount of emulsifier added is 0.5wt% to 4.5wt% of the alumina in the aluminum sol.

34. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The additive in step (3) is polyacrylamide.

35. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The concentration of the additive in step (3) is 1wt% to 5wt%, and the amount of additive added is 1wt% to 15wt% of the alumina in the aluminum sol.

36. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: In step (4), the molding process adopts the oil column molding method. The water-in-oil emulsion in step (4) is dripped into the oil column. The oil phase medium used in the oil injection molding process is either white oil or diesel oil, and the molding temperature is 90℃~110℃.

37. The method for preparing the petroleum resin hydrogenation catalyst according to claim 36, characterized in that: The oil phase medium used in the oil injection molding process is white oil, and the molding temperature is 95℃~105℃.

38. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: The aging process in step (4) has a temperature of 130℃~180℃, a pressure of 0.2~0.5MPa, and an aging time of 2~6h.

39. The method for preparing the petroleum resin hydrogenation catalyst according to claim 9, characterized in that: In step (4), the drying temperature is 100℃~150℃ and the drying time is 6~10 hours; the calcination temperature is 450℃~600℃ and the calcination time is 2~6 hours.

40. The application of the petroleum resin hydrogenation catalyst according to any one of claims 1-8 in the petroleum resin hydrogenation process.

41. The application according to claim 40, characterized in that: The petroleum resin is a C5 and / or C9 resin.

42. The application according to claim 40, characterized in that: The operating conditions for the hydrotreating process are: reaction pressure of 10–20 MPa, reaction temperature of 240℃–310℃, and liquid hourly space velocity of 0.3–2.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100–1000.

43. The application according to claim 40, characterized in that: Before use, petroleum resin hydrogenation catalysts need to undergo reduction treatment. The reduction pressure is 10-20 MPa, the reduction temperature is 400℃-600℃, and the reduction time is 8-15 h.

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