CN109395738B - Hydrogenation catalyst for carbon five petroleum resin and preparation method thereof - Google Patents
Hydrogenation catalyst for carbon five petroleum resin and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to a hydrogenation catalyst for carbon-five petroleum resin and a preparation method thereof, wherein the catalyst comprises a carrier and an active component, the carrier is an alumina-silica composite carrier, the active component comprises nickel oxide, molybdenum oxide and magnesium oxide, and the content of the alumina-silica composite carrier in the catalyst is 70-90 wt%, the content of the active component nickel oxide is 3-20 wt%, the content of the molybdenum oxide is 2-18 wt% and the content of the magnesium oxide is 0.1-6.5 wt% in percentage by mass. The catalyst C-V petroleum resin has high hydrogenation activity, strong sulfur resistance, good stability and good low-temperature activity.
Description
Technical Field
The invention relates to a hydrogenation catalyst for carbon five petroleum resin and a preparation method thereof.
Background
The petroleum resin is a product obtained by polymerizing a carbon five or carbon nine fraction which is a byproduct in the preparation of ethylene by cracking with a catalyst for polymerization or by thermal polymerization. It has a molecular weight of less than 2000, a softening point of 5-150 deg.C, and is a thermoplastic viscous liquid or solid. Petroleum resins have been used to improve the properties of various products, mainly in the fields of paints, adhesives, and inks, by blending with other polymer materials because of their tackifying properties, adhesive properties, and compatibility with other resin products. However, with the development of technology, the quality (hue, softening point, etc.) of petroleum resins is increasingly required. The hydrocarbon-five petroleum resin raw material has complex components (often has more chromogenic groups, gel, S, Cl and other impurities), is easy to cause toxic inactivation of the catalyst, is difficult to adsorb and activate due to poor mass transfer of a macromolecular polymer, and simultaneously avoids C-C hydrogenolysis fracture (which causes the softening point of a hydrogenated product to be reduced). Petroleum resin primary products in general are darker in color, less stable, and unstable to heat and oxidation, and particularly, due to the higher sulfur content, can generate an unpleasant odor when heated, which severely hinders their application in the field of high-end adhesive products. Resin refining generally adopts a hydrogenation method to saturate the residual double bonds and partial benzene rings in the resin so as to improve the color and the stability of the resin. The hydrogenated petroleum resin solves the problems of smell, chroma and oxidation stability of the petroleum resin, and greatly widens the application field of the petroleum resin. The hydrotreated carbon five petroleum resin is white or transparent, and has high stability and good intersolubility.
The resin hydrogenation catalyst mainly comprises noble metal and non-noble metal catalysts, wherein the early non-noble metal catalyst is a nickel catalyst loaded on diatomite or alumina-diatomite, and the weight percentage of nickel is 40-60%. U.S. Pat. No. 4,416,1395 discloses a nickel catalyst loaded on diatomite, which is hydrogenated at the reaction conditions of 230 ℃ at 210 ℃ and 3-9.1MPa for 5-7 hours, the product yield is about 95%, the Saybolt colorimetric value is about 25, the softening point is 180 ℃ at 150 ℃, and the bromine value is 1-3g Br2/100 g. The catalyst has the defects of low activity, high bromine number of the product and short service life. Later, supported nickel-tungsten sulfide or nickel-molybdenum sulfide catalysts with higher sulfur resistance were developed. European patent EP82716 discloses a supported nickel sulfide-tungsten catalyst, wherein the weight content of Ni is 2% -10%, and the weight content of W is 10% -25%. The reaction conditions are 250 ℃ and 330 ℃ and 15.2-20.3 MPa. The softening point of the resin product is 85-150 ℃, the Saybolt colorimetric value is 20-30, the bromine number is about 0, and the thermal stability of the product is obviously improved. The catalyst has strong sulfur resistance, and the defects of high reaction temperature and pressure are overcome. Chinese patent CN18033871A discloses a kettle-type catalytic hydrogenation and decoloration method for petroleum resin, which takes skeleton nickel as a catalyst, the dosage of the catalyst is 1-20 wt% of the petroleum resin, and the reaction conditions are as follows: the temperature is 100 ℃ and 250 ℃, the pressure is 1-10MPa, and the reaction time is 2-10 h. The catalyst has high activity, and the obtained resin product has light color and good thermal stability, and has the defects of large catalyst dosage and easy inactivation. The noble metal catalyst is mainly palladium catalyst and palladium-platinum catalyst, and the catalyst has the advantages of high activity, low start temperature, high product yield and high product quality. But has the disadvantages of sensitivity to poisons such as sulfur and the like and high susceptibility to poisoning and inactivation. Chinese patent CN102924659A discloses a two-stage fixed bed resin hydrogenation method, wherein the first stage catalyst is Ni/Al2O3, which is mainly used for removing sulfur in raw material resin. The second section is a noble metal Pt-Pd/Al2O3 hydrogenation catalyst, and the reaction conditions of the catalyst are as follows: the temperature is 250 ℃ and 350 ℃, the pressure is 2-6MPa, and the liquid space velocity is 1-5 h-1. The method gives full play to the advantages of the two-stage catalyst and prolongs the service life of the noble metal catalyst. But the disadvantage is that the reaction temperature is higher, resulting in lower softening point of the resin product, which affects the application range of the resin. CN201510431240.1 is used for preparation method and application of petroleum resin hydrogenation catalyst, and the catalytic performance of the catalyst is evaluated through a high-pressure fixed bed small test and pilot plant reaction device, and the catalyst is applied to industrial production. The catalyst is characterized in that active carbon or silicon dioxide is used as a carrier, active components of metal nickel, nickel molybdenum and nickel tungsten are loaded, the active components account for 30-50% by mass, an isometric impregnation method is adopted, the catalyst has good low-temperature hydrogenation activity when being used for C5 and C9 petroleum resins, the neutral carrier is adopted to reduce the breakage of molecular chains, the change range of the softening point of a product after hydrogenation is small, the impurity resistance and stability of the catalyst are excellent, and the bromine number and the chromaticity are within an ideal range.
CN201611257902.9 provides a hydrogenation method of carbon five petroleum resin, wherein the carbon five petroleum resin is dissolved in an organic solvent in a mixer, then preheated and enters a fixed bed hydrogenation reactor, a nickel-molybdenum hydrogenation catalyst is filled in the reactor, the hydrogenated material is sent to a stripping tower, the organic solvent extracted from the upper part is refined by a distillation tower and then recycled, and the carbon five petroleum resin is obtained at the bottom of the stripping tower; the catalyst prepared by the nickel-containing carrier with the specific crystal form can greatly improve the utilization rate of active metal and reduce the preparation difficulty of the catalyst, and meanwhile, the selected active components are added to play a synergistic role, so that the hydrocarbon hydrogen petroleum resin with low bromine value and good chromaticity and stability can be prepared.
In summary, the problems of insufficient antitoxic ability or greatly reduced softening point of hydrogenated products caused by overhigh hydrogenolysis activity of C-C bonds of the conventional C-V petroleum resin hydrogenation catalyst are technical bottlenecks restricting the development of the hydrogenation catalyst. Therefore, it is necessary to develop a catalyst with high hydrogenation activity, high sulfur impurity resistance and good activity stability.
Disclosure of Invention
The invention provides a hydrogenation catalyst for carbon five petroleum resin and a preparation method thereof, the catalyst petroleum resin has high hydrogenation activity, strong sulfur resistance, good stability, no easy shedding and crushing of active components, good low-temperature activity, long production running period, light color of the obtained resin product and good thermal stability.
The catalyst for hydrogenation of carbon-five petroleum resin comprises a carrier and an active component, wherein the carrier is an alumina-silica composite carrier, the active component comprises nickel oxide, molybdenum oxide and magnesium oxide, the alumina-silica composite carrier in the catalyst accounts for 70-90 wt%, the active component nickel oxide accounts for 3-20 wt%, the molybdenum oxide accounts for 2-18 wt%, the magnesium oxide accounts for 0.1-6.5 wt%, the alumina-silica composite carrier contains a lanthanum cerium zirconium oxide solid solution, the lanthanum cerium zirconium oxide solid solution accounts for 3-28 wt%, and the alumina-silica composite carrier contains 55-86 wt%.
Preferably, the hydrogenation catalyst for the hydrocarbon-modified petroleum resin comprises 3-17 wt% of nickel oxide, 4-16 wt% of molybdenum oxide and 0.1-4.5 wt% of magnesium oxide as active components.
The preparation method of the alumina-silica composite carrier comprises the following steps:
(a) uniformly mixing 50-70% of aluminum-containing compound and silicon-containing compound, and adding inorganic acid solution and rubber latex to obtain a mixture (1) containing aluminum and silicon; (b) mixing the rest 30-50% of the aluminum-containing compound with the lanthanum-cerium-zirconium oxide solid solution, and adding an inorganic acid solution and rubber latex to obtain an aluminum-containing and lanthanum-cerium-zirconium oxide solid solution mixture (2); calculated by oxide, the mass percentage of the rubber latex in the mixture (1) containing aluminum and silicon is more than 2 times of that in the mixture (2) containing aluminum and lanthanum-cerium-zirconium oxide solid solution; (c) and slowly adding the mixture (2) into the mixture (1), stirring and reacting for 1-3 hours, and obtaining the alumina-silica composite carrier through molding, drying and roasting. The silicon-containing compound is one or more of silica gel, sodium silicate or silica micropowder. The aluminum-containing compound is one or more of pseudo-boehmite, alumina, sodium metaaluminate and aluminum sulfate, and also can be one or more of kaolin, rectorite and montmorillonite. The alumina-silica composite carrier contains the lanthanum cerium zirconium oxide solid solution, the mass percentage of the rubber latex in the mixture (1) containing aluminum and silicon is more than 2 times of that of the rubber latex in the mixture (2) containing aluminum and lanthanum cerium zirconium oxide solid solution, and the nickel, molybdenum and magnesium active component is loaded. The inorganic acid is nitric acid, citric acid, etc.
In a further improvement, the preparation method of the alumina-silica composite carrier comprises the following steps:
(a) uniformly mixing 50-70% of aluminum-containing compound and silicon-containing compound, and adding inorganic acid solution, rubber latex and polyvinyl alcohol to obtain a mixture (1) containing aluminum and silicon; (b) mixing the rest 30-50% of the aluminum-containing compound with a lanthanum-cerium-zirconium oxide solid solution, and adding an inorganic acid solution, rubber latex and polyvinyl alcohol to obtain an aluminum-containing and lanthanum-cerium-zirconium oxide solid solution mixture (2); calculated by oxide, the mass percentage of the rubber latex and the polyvinyl alcohol in the mixture (1) containing aluminum and silicon is more than 1.6 times that of the rubber latex and the polyvinyl alcohol in the mixture (2) containing aluminum and lanthanum, cerium and zirconium oxide solid solutions; (c) and slowly adding the mixture (2) into the mixture (1), stirring and reacting for 1-3 hours, and obtaining the alumina-silica composite carrier through molding, drying and roasting. The silicon-containing compound is one or more of silica gel, sodium silicate or silica micropowder. The aluminum-containing compound is one or more of pseudo-boehmite, alumina, sodium metaaluminate and aluminum sulfate, and also can be one or more of kaolin, rectorite and montmorillonite. Rubber latex and polyvinyl alcohol are added into the mixture (1) containing aluminum and silicon and the solid solution mixture (2) containing aluminum and lanthanum, cerium and zirconium oxides, and the mass percentage of the rubber latex and the polyvinyl alcohol in the mixture (1) containing aluminum and silicon is more than 1.6 times that of the rubber latex and the polyvinyl alcohol in the solid solution mixture (2) containing aluminum and lanthanum, cerium and zirconium oxides; the catalyst has strong sulfur resistance, good low-temperature activity and high hydrogenation activity, and the obtained resin product has light color and good thermal stability.
The lanthanum-cerium-zirconium oxide solid solution La of the inventionxCeyZr1-xO2(0<x<1,0<y<1) The preparation method comprises the following steps: weighing a certain amount of cerium nitrate, lanthanum nitrate and zirconium nitrate according to a stoichiometric ratio to prepare a mixed solution, adding rubber latex, dropwise adding an ammonia water solution into the mixed solution under the condition of continuously stirring to perform coprecipitation reaction, and then performing suction filtration, drying, roasting and grinding to obtain the lanthanum-cerium-zirconium oxide solid solution. The rubber latex is preferably a polybutadiene rubber emulsion. The addition amount of the rubber latex accounts for 1-40 wt% of the mass of the lanthanum-cerium-zirconium oxide solid solution. Under the condition of high temperature, the nickel and the alumina oxide can generate strong interaction to generate a spinel structure, thereby leading the activity of the catalyst to be obviously reduced. The resin hydrogenation catalyst carrier comprises a lanthanum-cerium-zirconium oxide solid solution containing rubber latex, which is favorable for inhibiting the generation of nickel-aluminum spinel and the deterioration of the surface strength of the catalyst under the high-temperature condition, and has the advantages of difficult falling and crushing of active components and good activity stability.
The preparation method of the petroleum resin hydrogenation catalyst comprises the following steps: preparing soluble salt containing active components into solution, impregnating an alumina-silica composite carrier, drying and roasting to obtain the petroleum resin hydrogenation catalyst.
The petroleum resin hydrogenation catalyst obtained by drying and roasting is obtained by drying at the temperature of 120-150 ℃ for 4-8 hours and roasting at the temperature of 450-650 ℃ for 6-10 hours.
Detailed Description
The hydrogenation catalyst for petroleum resin and the preparation method of the present invention are further described in detail by examples and comparative examples. These examples should not be construed as limiting the invention. The main raw material sources for preparing the catalyst are as follows: the reagents of the invention are all commercial products.
Example 1
1) Weighing a certain amount of cerium nitrate, lanthanum nitrate and zirconium nitrate according to a stoichiometric ratio to prepare a mixed solution, adding polybutadiene rubber emulsion, dropwise adding an ammonia water solution into the mixed solution under the condition of continuous stirring to perform coprecipitation reaction, and then performing suction filtration, drying, roasting and grinding to obtain the lanthanum-cerium-zirconium oxide solid solution. The addition amount of the polybutadiene rubber emulsion accounts for 28 wt% of the mass of the lanthanum-cerium-zirconium oxide solid solution.
2) The preparation method of the alumina-silica composite carrier comprises the following steps:
(a) uniformly mixing 240 g of pseudo-boehmite with 120g of silicon micropowder, and adding a nitric acid solution and 86g of polybutadiene rubber emulsion to obtain a mixture (1) containing aluminum and silicon; (b)160g of pseudo-boehmite and 70g of lanthanum cerium zirconium oxide solid solution are mixed, and then inorganic acid solution and 14g of polybutadiene rubber emulsion are added to obtain an aluminum-containing and lanthanum cerium zirconium oxide solid solution mixture (2); (c) and slowly adding the mixture (2) into the mixture (1), stirring for reacting for 3 hours, and obtaining the alumina-silica composite carrier through molding, drying and roasting.
3) Preparing nickel nitrate, magnesium nitrate and ammonium molybdate into a solution, impregnating an alumina-silica composite carrier, drying at 130 ℃ for 5 hours, and roasting at 580 ℃ for 7 hours to obtain the catalyst, wherein the composition of the catalyst is shown in Table 1.
Example 2
The preparation method of the lanthanum-cerium-zirconium oxide solid solution is the same as that of the example 1, and the polybutadiene rubber emulsion is added in an amount accounting for 32 wt% of the mass of the lanthanum-cerium-zirconium oxide solid solution. The alumina-silica composite carrier was prepared in the same manner as in example 1, in terms of oxides, both the aluminum and silicon containing mixture (1) and the aluminum and lanthanum cerium zirconium oxide solid solution mixture (2) were added with rubber latex and polyvinyl alcohol, and the mass percentage of the rubber latex and polyvinyl alcohol in the aluminum and silicon containing mixture (1) was higher than 2 times that of the rubber latex and polyvinyl alcohol in the aluminum and lanthanum cerium zirconium oxide solid solution mixture (2). The catalyst was prepared in the same manner as in example 1, and the composition of the catalyst is shown in Table 1.
Example 3
The preparation method of the lanthanum-cerium-zirconium oxide solid solution is the same as that of the example 1, and the polybutadiene rubber emulsion is added in an amount which is 24 wt% of the mass of the lanthanum-cerium-zirconium oxide solid solution. The alumina-silica composite carrier was prepared in the same manner as in example 1, in terms of oxides, both the aluminum and silicon containing mixture (1) and the aluminum and lanthanum cerium zirconium oxide solid solution mixture (2) were added with rubber latex and polyvinyl alcohol, and the mass percentage of the rubber latex and polyvinyl alcohol in the aluminum and silicon containing mixture (1) was higher than 3.4 times that of the rubber latex and polyvinyl alcohol in the aluminum and lanthanum cerium zirconium oxide solid solution mixture (2). The catalyst was prepared in the same manner as in example 1, and the composition of the catalyst is shown in Table 1.
Comparative example 1
1) The preparation method of the alumina-silica composite carrier comprises the following steps:
(a) uniformly mixing 240 g of pseudo-boehmite with 120g of silicon micropowder, and adding a nitric acid solution and 86g of polybutadiene rubber emulsion to obtain a mixture (1) containing aluminum and silicon; (b) adding an inorganic acid solution and 14g of polybutadiene rubber emulsion into 160g of pseudo-boehmite to obtain an aluminum-containing mixture (2); (c) and slowly adding the mixture (2) into the mixture (1), stirring for reacting for 3 hours, and obtaining the alumina-silica composite carrier through molding, drying and roasting.
2) Nickel nitrate, magnesium nitrate and ammonium molybdate were mixed into a solution, the alumina-silica composite carrier was impregnated, dried at 130 ℃ for 5 hours, and calcined at 580 ℃ for 7 hours to obtain comparative catalyst 1, the composition of which is shown in table 1.
Comparative example 2
1) Weighing a certain amount of cerium nitrate, lanthanum nitrate and zirconium nitrate according to a stoichiometric ratio to prepare a mixed solution, adding polybutadiene rubber emulsion, dropwise adding an ammonia water solution into the mixed solution under the condition of continuous stirring to perform coprecipitation reaction, and then performing suction filtration, drying, roasting and grinding to obtain the lanthanum-cerium-zirconium oxide solid solution. The addition amount of the polybutadiene rubber emulsion accounts for 28 wt% of the mass of the lanthanum-cerium-zirconium oxide solid solution.
2) The preparation method of the alumina-silica composite carrier comprises the following steps:
(a) uniformly mixing 400 g of pseudo-boehmite, 70g of lanthanum cerium zirconium oxide solid solution and 120g of silicon micropowder, adding a nitric acid solution and 100g of polybutadiene rubber emulsion, stirring and reacting for 3 hours, and obtaining the alumina-silica composite carrier through molding, drying and roasting.
3) Nickel nitrate, magnesium nitrate and ammonium molybdate were mixed into a solution, the alumina-silica composite carrier was impregnated, dried at 130 ℃ for 5 hours, and calcined at 580 ℃ for 7 hours to obtain comparative catalyst 2, the composition of which is shown in table 1.
Hydrogenation reaction of resin
The raw material is ethylene cracking C5Petroleum resin with Gardener color of 9, bromine number of 21.3gBr/100g oil, S content of 43.2 mug. g-1The softening point 118.
The prepared catalysts 1-3 and the comparative catalyst are respectively filled in a fixed bed reactor, the catalyst is reduced by hydrogen firstly, the reduction temperature is 210 ℃, the hydrogen partial pressure is 2.5MPa, the hydrogen flow is 260mL/min, and the reduction time is 10 hours. After the reduction is finished, cyclohexane is used for dissolving C5 petroleum resin as a raw material, hydrogenation reaction is carried out, and the reaction process conditions are as follows: the temperature of the reactor is 250 ℃, the reaction pressure is 7.0MPa, and the volume isSpace velocity of 1.5h-1Hydrogen to oil volume ratio 280. The hydrogenated product is subjected to reduced pressure distillation to remove cyclohexane to obtain hydrogenated petroleum resin, and the properties of the catalyst reaction product are shown in Table 2. The catalyst 1-3 has strong sulfur resistance, good low-temperature activity, high hydrogenation activity, light color of the obtained resin product and good thermal stability. The comparative catalyst had poor activity, poor sulfur resistance, and the resin product color and thermal stability were inferior to the catalyst.
Table 1 example/comparative catalyst composition/wt%
| Examples/comparative examples | Nickel oxide wt.% | Molybdenum oxide wt% | Magnesium oxide wt.% |
| Example 1 | 13 | 8 | 0.2 |
| Example 2 | 15 | 10 | 0.1 |
| Example 3 | 12 | 11 | 0.3 |
| Comparative example 1 | 13 | 8 | 0.2 |
| Comparative example 2 | 13 | 8 | 0.2 |
TABLE 2 catalyst and comparative catalyst reaction results
The results after 500 hours of reaction of catalysts 1-3 are shown in Table 3. The catalyst has the advantages that the bromine number of 1-3 is not changed greatly, the activity is not obviously reduced, the catalyst has strong sulfur resistance and good stability, the introduction of the lanthanum-cerium-zirconium oxide solid solution into the catalyst is favorable for inhibiting the generation of nickel-aluminum spinel under the high-temperature condition and the deterioration of the surface strength of the catalyst, the active components are not easy to fall off and break, and the activity stability is good. Comparative catalyst 1, the activity of which is remarkably reduced after 60 hours of reaction, has bromine number of 12.32gBr 100g-1Sulfur content 13.6. mu.g.g-1The results show that the catalyst has poor sulfur resistance and poor stability, and the comparative catalyst 1 is broken significantly when it is unloaded from the reactor. Comparative example catalyst 2 reaction for 60 hours bromine number 7.87gBr 100g-1Sulfur content 8.2. mu.g.g-1The catalyst activity is reduced, the sulfur resistance is weak, and the color and the thermal stability of the resin product are poor.
TABLE 3 results of the catalytic reaction
Claims (6)
1. The hydrogenation catalyst for carbon-five petroleum resin is characterized by comprising a carrier and an active component, wherein the carrier is aluminaThe catalyst comprises an alumina-silica composite carrier, an active component and a carrier matrix, wherein the active component comprises nickel oxide, molybdenum oxide and magnesium oxide, the content of the alumina-silica composite carrier in the catalyst is 70-90 wt%, the content of the active component nickel oxide is 3-20 wt%, the content of the molybdenum oxide is 2-18 wt%, the content of the magnesium oxide is 0.1-6.5 wt%, and the alumina-silica composite carrier comprises a lanthanum cerium zirconium oxide solid solution LaxCeyZr1-xO2，0<x<1， 0<y<1, the content of the lanthanum-cerium-zirconium oxide solid solution is 3-28 wt%, and the content of alumina in the alumina-silica composite carrier is 55-86 wt%; the preparation method of the alumina-silica composite carrier comprises the following steps: (a) uniformly mixing 50-70 wt% of an aluminum-containing compound and a silicon-containing compound, and adding an inorganic acid solution and rubber latex to obtain a mixture (1) containing aluminum and silicon; (b) mixing the rest 30-50 wt% of aluminum-containing compound with the lanthanum-cerium-zirconium oxide solid solution, and adding an inorganic acid solution and rubber latex to obtain an aluminum-containing and lanthanum-cerium-zirconium oxide solid solution mixture (2); calculated by oxide, the mass percentage of the rubber latex in the mixture (1) containing aluminum and silicon is more than 2 times of that in the mixture (2) containing aluminum and lanthanum-cerium-zirconium oxide solid solution; (c) slowly adding the mixture (2) into the mixture (1), stirring and reacting for 1-3 hours, and obtaining an alumina-silica composite carrier through molding, drying and roasting; the lanthanum-cerium-zirconium oxide solid solution LaxCeyZr1-xO2， 0<x<1， 0<y<The preparation method comprises the following steps: weighing a certain amount of cerium nitrate, lanthanum nitrate and zirconium nitrate according to a stoichiometric ratio to prepare a mixed solution, adding rubber latex, dropwise adding an ammonia water solution into the mixed solution under the condition of continuously stirring to perform coprecipitation reaction, and then performing suction filtration, drying, roasting and grinding to obtain a lanthanum-cerium-zirconium oxide solid solution; the preparation method of the carbon five petroleum resin hydrogenation catalyst comprises the following steps: preparing soluble salt containing active components into solution, impregnating an alumina-silica composite carrier, drying and roasting to obtain the carbon five petroleum resin hydrogenation catalyst.
2. The hydrogenation catalyst for carbon five petroleum resin as claimed in claim 1, wherein the catalyst active component comprises nickel oxide 3-17 wt%, molybdenum oxide 4-16 wt%, and magnesium oxide 0.1-4.5 wt%.
3. The hydrogenation catalyst for carbon five petroleum resin as claimed in claim 1, wherein the preparation method of the alumina-silica composite carrier is as follows: (a) uniformly mixing 50-70 wt% of an aluminum-containing compound and a silicon-containing compound, and adding an inorganic acid solution, rubber latex and polyvinyl alcohol to obtain a mixture (1) containing aluminum and silicon; (b) mixing the rest 30-50 wt% of aluminum-containing compound with a lanthanum-cerium-zirconium oxide solid solution, and adding an inorganic acid solution, rubber latex and polyvinyl alcohol to obtain an aluminum-containing and lanthanum-cerium-zirconium oxide solid solution mixture (2); calculated by oxide, the mass percentage of the rubber latex and the polyvinyl alcohol in the mixture (1) containing aluminum and silicon is more than 2 times that of the rubber latex and the polyvinyl alcohol in the mixture (2) containing aluminum and lanthanum, cerium and zirconium oxide solid solutions; (c) and slowly adding the mixture (2) into the mixture (1), stirring and reacting for 1-3 hours, and obtaining the alumina-silica composite carrier through molding, drying and roasting.
4. The hydrogenation catalyst for carbon five petroleum resin as claimed in any one of claims 1 or 3, wherein the silicon-containing compound is one or more of silica gel, sodium silicate or silica micropowder.
5. The catalyst for hydrogenation of carbon-five petroleum resin as claimed in any one of claims 1 or 2, wherein the aluminum-containing compound is one or more of pseudo-boehmite, alumina, sodium metaaluminate and aluminum sulfate.
6. The catalyst for hydrogenation of carbon-five petroleum resin as claimed in any one of claims 1 or 2, wherein the aluminum-containing compound is one or more of kaolin, rectorite and montmorillonite.
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| CN104117359A (en) * | 2013-04-27 | 2014-10-29 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
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| CN108236968A (en) * | 2016-12-27 | 2018-07-03 | 中国石油天然气股份有限公司 | A kind of alumina support of containing mesopore/macropore and preparation method thereof |
| CN108264586A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of method of hydrotreating of C 5 petroleum resin |
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| JP2011072933A (en) * | 2009-09-30 | 2011-04-14 | Jgc Catalysts & Chemicals Ltd | Hydrogenation catalyst of hydrocarbon and method for preparing the same |
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| CN101380590A (en) * | 2008-07-13 | 2009-03-11 | 中国石油兰州石油化工公司 | Selective hydrogenation catalyst for carbon five fraction and preparation and use thereof |
| CN101700494A (en) * | 2009-10-22 | 2010-05-05 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst and use thereof |
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