A catalyst for catalyzing hydrogenation of DCPD petroleum resin, a preparation method and application thereof

Abstract

The application relates to a catalyst for catalyzing DCPD petroleum resin hydrogenation and a preparation method and application thereof, and belongs to the technical field of catalyst preparation. The catalyst takes nickel as an active component, adds a certain amount of molybdenum additives, and takes diatomite as a carrier. The preparation method is as follows: diatomite is added into a nickel salt solution, a precipitant solution is added, stirring is carried out, then ammonium molybdate is added, and the precursor is obtained through suction filtration and drying; the Ni-Mo / diatomite catalyst is obtained by reducing the precursor in a tube furnace. The catalyst has the characteristics of high catalytic activity, good stability, easy separation and the like, can catalyze DCPD petroleum resin hydrogenation under mild reaction conditions, realizes high conversion rate and high selectivity, the catalyst can still maintain high activity after being used for multiple times, and is suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of preparation of nickel-based catalysts, and particularly relates to a catalyst for producing DCPD petroleum resin and a preparation method thereof. BACKGROUND

[0002] The industrial production of petroleum resin began in the United States in 1950, and the output has been steadily increasing in the past few decades. According to the different properties of the raw materials, petroleum resin can be classified into four main types, namely aromatic petroleum resin, aliphatic petroleum resin, DCPD petroleum resin, and modified petroleum resin. DCPD petroleum resin, also known as dicyclopentadiene petroleum resin, is polymerized from dicyclopentadiene under high temperature and high pressure conditions. DCPD petroleum resin is widely used as an additive in adhesives, coatings, printing inks, rubber additives, etc. However, the product still has the following defects: such as dark color, unpleasant odor, high unsaturated bond content, easy oxidation, poor thermal stability, and poor adhesion, and it cannot be well dissolved in other resin matrix. After hydrogenation reaction, the unsaturation degree of DCPD petroleum resin is significantly reduced, the color is light, there is no special odor, and it can be well compatible with SIS, SBS and EVA. In addition to being used in tackifiers, pressure-sensitive adhesives, inks and rubbers, etc., it can also be used in special adhesives used in the production of light shoe adhesive, food packaging products, disposable paper diapers and women's sanitary napkins, etc. Therefore, considering the current market demand, hydrogenation modification of DCPD petroleum resin has important industrial significance.

[0003] Patents US4,384,080 and US4.952,639 describe petroleum resin hydrogenation methods using noble metals such as nickel, palladium, platinum, rhenium, ruthenium, etc. as hydrogenation catalysts, generally using single-component metal as the active component of the catalyst. Patent US4,540,480 introduces a petroleum resin hydrogenation method, and the active component of the catalyst used is a combination of the above-mentioned noble metals, and the carrier of the catalyst is generally alumina. It is claimed that the catalyst used has high activity and long service life, and the color of the obtained hydrogenated petroleum resin is 1#. These existing petroleum resin hydrogenation methods have a significant effect on reducing the unsaturated bond content of dicyclopentadiene resin, but are not very ideal in improving the color of the resin. In particular, the dicyclopentadiene obtained by separation of carbon five fraction byproduct from petroleum cracking contains a large amount of impurities, and the purity is usually only 75-85wt%, and other impurities contained include unknown dimers, trimers, indenes, isoprene dimers, benzene and toluene, etc. The dicyclopentadiene petroleum resin prepared not only has high unsaturated hydrocarbon bond content, but also has a dark color. This dicyclopentadiene petroleum resin cannot obtain hydrogenated resin with ideal color by using the existing general petroleum resin hydrogenation method.

[0004] The catalysts for hydrogenation of petroleum resin mainly include noble metal and non-noble metal. Generally, the reaction conditions of non-noble metal catalysts are more severe. CN201110234154.3, CN201410705478.4, CN202011039259.9, CN201210223685.7, CN200610099032.7, CN200610099032.7, Pd supported on alumina metal catalyst, and modified by doping metals or oxides in the catalyst system. Non-noble metal catalysts generally use nickel as the active component. CN201510886175.1 uses Ni as the active component and magnesium oxide as the carrier. CN202210034140.5 uses Ni as the active component and alumina as the carrier. CN201910023118.9 and CN202011022171.6 use Ni as the active component, alumina as the carrier, and modify the nickel system by doping active components such as metals or metal oxides. Japanese patents JP3265369 and JP 3289326 use nickel supported on diatomite catalyst, and modify the system by adding barium, calcium, magnesium, copper and other elements. SUMMARY

[0005] The application provides a catalyst for catalyzing petroleum resin and a preparation method thereof. The catalyst uses nickel as the active component, adds a certain content of molybdenum component for modification, and uses diatomite as the carrier. Due to the synergistic catalysis of nickel-molybdenum and diatomite, the activity and sulfur resistance of the catalyst are obviously improved, and the catalyst has good stability. Under relatively mild reaction conditions, high conversion rate and low color phase of THDCPD petroleum resin can be realized by catalytic hydrogenation of DCPD petroleum resin, and the catalyst still has activity after multi-kettle application, effectively solving the problem of sulfur poisoning of the catalyst.

[0006] The application is achieved by the following technical solutions:

[0007] A catalyst for catalyzing DCPD petroleum resin hydrogenation to prepare THDCPD petroleum resin, which uses nickel nanoparticles as the active component, diatomite as the carrier, and molybdenum as the additive; the catalyst has the following mass percentage composition: nickel 30-50%, diatomite 50-80%, and molybdenum 5-20%.

[0008] A preparation method of a catalyst for catalyzing DCPD petroleum resin hydrogenation to prepare THDCPD petroleum resin, which includes the following steps:

[0009] (1) Prepare a nickel salt solution with a mass concentration of 1-40%, and under stirring conditions, add the diatomite carrier to the nickel salt solution, and stir at 25-100℃ for 0.5-24h;

[0010] (2) to the above step, add 1-1000 μL silica sol, stirring at 25-100 ℃ for 0.5-24 h; then add 1-40% of a precipitant solution under stirring, weigh 1-100 g of ammonium molybdate and add into the mixture, stirring at 25-100 ℃ for 0.5-24 h; (3) filter, dry, and then place in a tube furnace, reduce at 300-700 ℃ under hydrogen atmosphere for 1-24 h, to obtain a Ni-Mo supported diatomite catalyst.

[0011] The nickel salt solution is a solution of one or several of nickel nitrate, nickel sulfate, nickel chloride or nickel acetate.

[0012] The precipitant solution is a solution of one or several of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate, ammonia water or urea.

[0013] The molar ratio of the precipitant solution to the nickel salt solution is (1-5):1.

[0014] The catalyst is applied to the hydrogenation of DCPD petroleum resin to prepare THDCPD petroleum resin.

[0015] The preparation process of the hydrogenation of DCPD petroleum resin to prepare THDCPD petroleum resin is as follows:

[0016] The catalyst is reacted with DCPD petroleum resin in a solvent for 1-10 h; the reaction temperature is 200-260 ℃, the hydrogen pressure is 5-7 MPa, and the reaction device is a kettle type reactor, a loop reactor or a fixed bed reactor.

[0017] The mass ratio of the catalyst to DCPD petroleum resin is (0.02-0.6):1.

[0018] The solvent is one or several of decalin, tetrahydrofuran, dioxane, petroleum ether, solvent oil, cyclohexane, methylcyclohexane or n-heptane.

[0019] The mass ratio of the solvent to DCPD petroleum resin is 1:1-20:1.

[0020] The present application provides a catalyst for catalyzing the hydrogenation of DCPD petroleum resin to prepare THDCPD petroleum resin, which comprises nickel as an active component, diatomite as a carrier and a certain amount of molybdenum as an additive. The mass percentage composition of the catalyst is as follows: nickel is 1-60%, preferably 20-50%; diatomite is 40-99%, preferably 50-80%. The synergistic catalysis of nickel-molybdenum and diatomite and the principle of molybdenum as an additive to solve sulfur poisoning can realize efficient catalytic hydrogenation to prepare hydrogenated resin.

[0021] In addition, the present application also provides a method for preparing the above nickel catalyst, which comprises the following steps:

[0022] 1) prepare a nickel salt solution with a mass concentration of 1-40%, stir at 25-100℃ for 1-24h, add diatomite carrier to the above nickel salt solution, stir at 25-100℃ for 1-24h;

[0023] 2) add 1-100μL silica sol to step 1), stir at 25-100℃ for 0.5-24h; prepare a precipitant solution with a mass concentration of 1-40%, add to the mixture obtained in step 1) under stirring, weigh 1-100g ammonium molybdate and add to the mixture, stir at 25-100℃ for 0.5-24h;

[0024] 3) filter the mixture obtained in step 2), dry the filter cake at 25-180℃, then place in a tube furnace, reduce at 300-700℃ under hydrogen atmosphere for 1-24h, to obtain a nickel-molybdenum supported diatomite catalyst.

[0025] Further, in the above preparation method, the nickel salt in step 1) is selected from any one or combination of nickel nitrate, nickel sulfate, nickel chloride or nickel acetate.

[0026] Further, in the above preparation method, the diatomite in step 1) is selected from diatomite filter aid, and the median particle size of the fused product is 13μm (excellent performance).

[0027] Further, in the above preparation method, the precipitant in step 2) is selected from any one or combination of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate, ammonia water or urea; the molar ratio of precipitant to nickel metal salt is (1-5):1.

[0028] The application further provides a method for catalyzing hydrogenation of DCPD petroleum resin by using the above catalyst: the catalyst and DCPD petroleum resin are reacted in a solvent for 0.5-10h, preferably 1-3h; the reaction temperature is 160-260℃, preferably 200-260℃; the hydrogen pressure is 5-15MPa, preferably 5-7MPa; the mass ratio of catalyst to DCPD petroleum resin is 0.02-0.2:1, preferably 0.05-0.2:1; and the reaction device is a kettle reactor, a loop reactor or a fixed bed reactor.

[0029] The application has the following advantages: 1. The supported catalyst is prepared by using cheap nickel, has similar reaction activity to noble metal catalysts, and greatly reduces the production cost of THDCPD petroleum resin catalytic hydrogenation;

[0030] 2. In the reaction of preparing THDCPD petroleum resin by catalytic hydrogenation of DCPD petroleum resin, the mild reaction conditions of temperature 160-260℃ and pressure 5-15 MPa are adopted, the defects of high temperature and high pressure in the traditional process are overcome, the production process operation is simplified, the equipment requirement is reduced, and the overall economic cost is obviously decreased. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 are scanning electron micrographs of diatomite (a. b.) and the prepared Ni-diatomite catalyst (c. d.) of Example 1.

[0032] Figure 2 is a transmission electron micrograph of the Ni-Mo / diatomite catalyst prepared in Example 6.

[0033] Figure 3 is an X-ray diffraction pattern of the Ni-Mo / diatomite catalyst prepared in Example 6. DETAILED DESCRIPTION

[0034] The reaction device used in the present application is a kettle reactor, a fixed bed reactor or a loop reactor. Suitable process conditions are as follows: the catalyst is reacted with DCPD petroleum resin in a solvent for 0.5-10 h, preferably 1-3 h; the reaction temperature is 100-260℃, preferably 180-260℃; the hydrogen pressure is 0.1-3 MPa, preferably 0.5-1.5 MPa; the mass ratio of catalyst to DCPD petroleum resin is 0.02-0.2:1, preferably 0.05-0.2:1; the reaction solvent is one or a mixture of several of decalin, tetrahydrofuran, petroleum ether, solvent oil, cyclohexane, methylcyclohexane, n-heptane, and the mass ratio of solvent to DCPD petroleum resin is 5:1.

[0035] In the examples, the test methods of various indexes are as follows:

[0036] Reaction hydrogenation rate: nuclear magnetic quantitative analysis

[0037] Color: iron-cobalt colorimeter; reference standard ASTM D-1544.

[0038] Table 1. Properties of petroleum resin

[0039] Resin type Colour # DCPD petroleum resin 7

[0040] The present application is further illustrated below in conjunction with examples.

[0041] Nickel nitrate is purchased from Dalian General Chemical Co., Ltd.: Ni(NO3)2·6H2O content is not less than 98%;

[0042] Diatomite is purchased from Dalian General Chemical Co., Ltd.: diatomite filter aid, fusion agent sintered product, median particle size: 13 μm;

[0043] Urea was purchased from Guangdong Guanghua Science and Technology Co., Ltd.: CO(NH2)2 content not less than 99.0%.

[0044] Example 1

[0045] Preparation of Ni supported diatomite catalyst: 20 g of nickel nitrate was dissolved in 70 mL of deionized water to prepare a 22% nickel nitrate aqueous solution, stirred at 25°C for 1 h, and then 5 g of diatomite with different particle sizes was added and stirred for another 1 h. 600 μL of silica sol was added and stirred for 1 h, and then the temperature was raised to 90°C. 10.5 g of urea was dissolved in 70 mL of distilled water to prepare a 13% urea solution, which was added into the above solution at a constant rate using a peristaltic pump, and the temperature was raised to 90°C. The mixture was stirred for 24 h. The obtained solution was washed several times and suction filtered to obtain a semi-solid filter cake, which was dried in a drying oven for 20 h to obtain a precursor. The precursor was placed in a hydrogen atmosphere and reduced at 500°C for 24 h to obtain the Ni supported diatomite catalyst.

[0046] Catalyst performance test: A tank reactor was used to apply the catalyst to petroleum resin hydrogenation, and the reaction conditions were as follows: 6 g of DCPD petroleum resin, 15 mL of cyclohexane solvent, and 0.25 g of Ni / diatomite catalyst. The reaction results were as follows:

[0047] Table 2. Hydrogenation results of DCPD petroleum resin

[0048] Catalyst Reaction temperature / °C Reaction pressure / MPa Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin (3.5 μm) 220 7 1 86 8.5 Ni / kaolin (13 μm) 220 7 1 97 3

[0049] Screening of diatomite: Diatomite with particle sizes of 13 μm and 3.5 μm was used as the carrier of the catalyst, respectively. It was found that the catalyst prepared using diatomite with a particle size of 13 μm had higher activity, and therefore diatomite with a particle size of 13 μm was used as the carrier of the nickel-based catalyst in this article.

[0050] Example 2

[0051] Preparation of Ni supported diatomite catalyst: 20 g of nickel nitrate was dissolved in 70 mL of deionized water to prepare a 22% nickel nitrate aqueous solution, stirred at 25°C for 1 h, and then 5 g of diatomite was added and stirred for another 1 h. 600 μL of silica sol was added and stirred for 1 h, and then the temperature was raised to 90°C. 10.5 g of urea was dissolved in 70 mL of distilled water to prepare a 13% urea solution, which was added into the above solution at a constant rate using a peristaltic pump, and the temperature was raised to 90°C. The mixture was stirred for 24 h. The obtained solution was washed several times and suction filtered to obtain a semi-solid filter cake, which was dried in a drying oven for 20 h to obtain a precursor. The precursor was placed in a hydrogen atmosphere and reduced at 500°C for 24 h to obtain the Ni supported diatomite catalyst.

[0052] Catalyst performance test: The catalyst was applied to petroleum resin hydrogenation in a tank reactor, and the reaction conditions were as follows: 6 g of DCPD petroleum resin, 15 ml of cyclohexane solvent, and 0.25 g of Ni / diatomite catalyst. The reaction results were as follows:

[0053] Table 3. DCPD petroleum resin hydrogenation results

[0054]

[0055]

[0056] As can be seen from the above table, the Ni-loaded diatomite catalyst has better hydrogenation effect on DCPD petroleum resin at a reaction temperature of 220°C.

[0057] Example 3

[0058] Preparation of Ni-loaded diatomite catalyst: 20 g of nickel nitrate was dissolved in 70 mL of deionized water to prepare a 22% nickel nitrate aqueous solution, which was stirred at 25°C for 1 h, 5 g of diatomite was added and continued to be stirred for 1 h; 600 μL of silica sol was added and continued to be stirred for 1 h, and then the temperature was raised to 90°C. 10.5 g of urea was dissolved in 70 mL of distilled water to prepare a 13% urea solution, which was uniformly and quantitatively dropped into the above solution using a peristaltic pump, and the temperature was raised to 90°C, and stirred for 24 h. The obtained solution was suction filtered and washed three times to obtain a solid, which was placed in an oven for drying for 20 h to obtain a precursor. The precursor was placed in a hydrogen atmosphere, reduced at 500°C for 24 h to obtain the Ni-loaded diatomite catalyst.

[0059] Catalyst performance test: The catalyst was applied to petroleum resin hydrogenation in a tank reactor, and the reaction conditions were as follows: 6 g of DCPD petroleum resin, 15 ml of cyclohexane solvent, and 0.25 g of Ni / diatomite catalyst. The reaction results were as follows:

[0060] Table 4. DCPD petroleum resin hydrogenation results

[0061] Catalyst Reaction temperature / °C Reaction pressure / MPa Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin 220 4 1 86 11 Ni / kaolin 220 5 1 90 9 Ni / kaolin 220 6 1 95 3 Ni / kaolin 220 7 1 97 3

[0062] As can be seen from the above table, the Ni-loaded diatomite catalyst has better hydrogenation effect on DCPD petroleum resin at a reaction temperature of 220°C, and the same reaction time, and the effect is better with the increase of pressure.

[0063] Example 4

[0064] Preparation of Ni supported diatomite catalyst: 20 g of nickel nitrate was dissolved in 70 mL of deionized water to prepare a 22% nickel nitrate aqueous solution, which was stirred at 25°C for 1 h, 5 g of diatomite was added and stirring was continued for 1 h; 600 μL of silica sol was added and stirring was continued for 1 h, and then the temperature was raised to 90°C. 10.5 g of urea was dissolved in 70 mL of distilled water to prepare a 13% urea solution, which was quantitatively dropped into the above solution at a constant speed using a peristaltic pump. The temperature was raised to 90°C, and stirring was continued for 24 h. The obtained solution was suction filtered and washed three times to obtain a solid, which was placed in an oven for drying for 20 h to obtain a precursor. The precursor was placed in a hydrogen atmosphere, and reduction was carried out at 500°C for 24 h to obtain a Ni / diatomite catalyst.

[0065] Catalyst performance test: a kettle reactor was used, and the catalyst was applied to petroleum resin hydrogenation, and the reaction conditions were as follows: 6 g of DCPD petroleum resin, 15 ml of cyclohexane solvent, and 0.25 g of Ni / diatomite catalyst. The reaction results were as follows:

[0066] Table 5. DCPD petroleum resin hydrogenation results

[0067] Catalyst Resin mass / g Reaction temperature / °C Reaction pressure / MPa Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin 6 220 7 1 97 4 Ni / kaolin 5 220 7 1 98 3 Ni / kaolin 4 220 7 1 99 0 Ni / kaolin 3 220 7 1 99 0 Ni / kaolin 2 220 7 1 100 0

[0068] As can be seen from the above table, the resin hydrogenation rate gradually increased with the progress of the reaction, the color of the resin gradually became lighter, and finally stabilized at 0#.

[0069] Example 5

[0070] Preparation of Ni supported diatomite catalyst: 20 g of nickel nitrate was dissolved in 70 mL of deionized water to prepare a 22% nickel nitrate aqueous solution, which was stirred at 25°C for 1 h, 5 g of diatomite was added and stirring was continued for 1 h; 600 μL of silica sol was added and stirring was continued for 1 h, and then the temperature was raised to 90°C. 10.5 g of urea was dissolved in 70 mL of distilled water to prepare a 13% urea solution, which was quantitatively dropped into the above solution at a constant speed using a peristaltic pump. The temperature was raised to 90°C, and stirring was continued for 24 h. The obtained solution was suction filtered and washed three times to obtain a solid, which was placed in an oven for drying for 20 h to obtain a precursor. The precursor was placed in a hydrogen atmosphere, and reduction was carried out at 500°C for 24 h to obtain a Ni / diatomite catalyst.

[0071] Catalyst performance test: a kettle reactor was used, and the catalyst was applied to petroleum resin hydrogenation, and the reaction conditions were as follows: 6 g of DCPD petroleum resin, 15 ml of cyclohexane solvent, and 0.25 g of Ni / diatomite catalyst. The catalyst was repeatedly used, and the reaction results were as follows:

[0072] Table 6. Ni / diatomite life test

[0073] Number of reuses Catalyst Reaction time / h Hydrogenation rate / % Colour # 1 Ni / kaolin 1 97 3 2 Ni / kaolin 1 95 5 3 Ni / kaolin 1 93 6 4 Ni / kaolin 1 90 9

[0074] Example 6

[0075] Ni-Mo supported diatomite catalyst preparation: 20 g of nickel nitrate was dissolved in 70 mL of deionized water to prepare a 22% nickel nitrate aqueous solution, stirred at 25°C for 1 h, 5 g of diatomite was added and continued to stir for 1 h; 600 μL of silica sol was added and continued to stir for 1 h, then heated to 90°C. 10.5 g of urea was dissolved in 70 mL of distilled water to prepare a 13% urea solution, which was added to the above solution at a constant rate using a peristaltic pump, and a certain amount of ammonium molybdate was added to the mixed solution (5% Mo, 10% Mo, 15% Mo, 20% Mo), heated to 90°C, and stirred for 24 h. The obtained solution was suction filtered and washed three times to obtain a solid, which was placed in an oven to dry for 20 h to obtain a precursor. The precursor was placed in a hydrogen atmosphere and reduced at 500°C for 24 h to obtain a Ni-Mo supported diatomite catalyst.

[0076] Catalyst performance test: A tank reactor was used, and the catalyst was applied to petroleum resin hydrogenation. The reaction conditions were as follows: 6 g of DCPD petroleum resin, 15 ml of cyclohexane solvent, and 0.25 g of Ni-Mo supported diatomite catalyst. The reaction results were as follows:

[0077] Table 7. DCPD petroleum resin hydrogenation results

[0078] Catalyst Reaction temperature / °C Reaction pressure / MPa Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin 220 7 1 97 4 NiMo 5％ / diatomite 220 7 1 98 1 NiMo 10％ / diatomite 220 7 1 99 0 NiMo 15％ / diatomite 220 7 1 99 0 NiMo 20％ / diatomite 220 7 1 99 0

[0079] As can be seen from the above table, compared with the Ni supported diatomite catalyst, the catalyst modified by molybdenum has better DCPD petroleum resin hydrogenation effect, and the effect is continuously improved with the increase of molybdenum content; but when the molybdenum content increases to 10%, the catalytic performance basically no longer increases.

[0080] Example 7

[0081] Ni-Mo supported diatomite catalyst preparation: 20 g of nickel nitrate was dissolved in 70 mL of deionized water to prepare a 22% nickel nitrate aqueous solution, stirred at 25°C for 1 h, 5 g of diatomite was added and continued to stir for 1 h; 600 μL of silica sol was added and continued to stir for 1 h, then heated to 90°C. 10.5 g of urea was dissolved in 70 mL of distilled water to prepare a 13% urea solution, which was added to the above solution at a constant rate using a peristaltic pump, and a certain amount of ammonium molybdate was added to the mixed solution (5% Mo, 10% Mo, 15% Mo, 20% Mo), heated to 90°C, and stirred for 24 h. The obtained solution was suction filtered and washed three times to obtain a solid, which was placed in an oven to dry for 20 h to obtain a precursor. The precursor was placed in a hydrogen atmosphere and reduced at 500°C for 24 h to obtain a Ni-Mo supported diatomite catalyst.

[0082] Catalyst performance test: The catalyst was applied to petroleum resin hydrogenation in a tank reactor. The reaction conditions were as follows: 6 g of DCPD petroleum resin, 15 ml of cyclohexane solvent, and 0.25 g of Ni-Mo supported diatomite catalyst. The reaction results were as follows:

[0083] Table 8. Ni 44 -Mo 10 / diatomite life test

[0084]

[0085]

[0086] Example 8

[0087] Preparation of Ni-Mo supported diatomite catalyst: 20 g of nickel nitrate was dissolved in 70 mL of deionized water to prepare a 22% nickel nitrate aqueous solution, which was stirred at 25°C for 1 h, 5 g of diatomite was added and stirring was continued for 1 h; 600 μL of silica sol was added and stirring was continued for 1 h, and then the temperature was raised to 90°C. 10.5 g of urea was dissolved in 70 mL of distilled water to prepare a 13% urea solution, which was added to the above solution at a constant rate using a peristaltic pump, 5.62 g of ammonium molybdate was added to the mixed solution (10% Mo), the temperature was raised to 90°C, and stirring was continued for 24 h. The obtained solution was suction filtered and washed three times to obtain a solid, which was dried in an oven for 20 h to obtain a precursor. The precursor was placed in a hydrogen atmosphere, reduced at 500°C for 24 h to obtain a Ni-Mo supported diatomite catalyst.

[0088] Catalyst performance test: The catalyst was applied to petroleum resin hydrogenation in a tank reactor. The reaction conditions were as follows: 6 g of DCPD petroleum resin, 15 ml of cyclohexane solvent, and 0.25 g of Ni-Mo supported diatomite catalyst. The reaction results were as follows:

[0089] Table 9. Ni- diatomite and Ni-Mo 10％ / diatomite life test comparison

[0090] Number of reuses Catalyst Reaction time / h Hydrogenation rate / % Colour # 4 Ni / kaolin Ni / kaolin Ni / kaolin Ni / kaolin Catalyst Reaction temperature / °C Reaction pressure / MPa Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin Number of reuses Catalyst Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin Ni / kaolin Ni / kaolin Ni / kaolin Catalyst Reaction temperature / °C Reaction pressure / MPa Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin Number of reuses Catalyst Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin Ni / kaolin Ni / kaolin Ni / kaolin Catalyst Reaction temperature / °C Reaction pressure / MPa Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin Number of reuses Catalyst Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin Ni / kaolin Ni / kaolin Ni / kaolin Catalyst Reaction temperature / °C Reaction pressure / MPa Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin Number of reuses Catalyst Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin Ni / kaolin Ni / kaolin Ni / kaolin Catalyst Reaction temperature / °C Reaction pressure / MPa Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin Number of reuses Catalyst Reaction time / h Hydrogenation rate / % Colour # Ni / kaolin Ni / kaolin Ni / kaolin Ni / kaolin Catalyst Reaction temperature / °C Reaction pressure / MPa 1 90 9 4 Ni-Mo 10％ diatomite 1 93 4

[0091] Stability test results of Ni / diatomite catalyst and Ni-Mo / diatomite catalyst: After four cycles of the kettle experiment, the hydrogenation rate of the Ni supported diatomite catalyst decreased from 97% to 90%, and the color number increased from 3# to 9#. The hydrogenation rate of the Ni-Mo supported diatomite catalyst decreased from 99% to 93% after four cycles of the kettle experiment, and the color number increased from 0# to 4#. It is shown that the catalyst with Mo has higher activity and better stability.

Claims

1. Use of a catalyst, characterized in that: The catalyst is applied to the preparation of THDCPD petroleum resin by hydrogenation of DCPD petroleum resin; The catalyst takes nickel nanoparticles as active component, diatomite as carrier and molybdenum as additive; the mass percentage composition of the catalyst is as follows: 30-50% of nickel, 50-80% of diatomite and 5-20% of molybdenum; the mass sum of the above components is 100%; the particle size of the diatomite is 13 μm; The preparation method of the catalyst comprises the following steps: (1) preparing a nickel salt solution with a mass concentration of 1-40%, and adding the diatomite carrier into the nickel salt solution under stirring at 25-100 ℃ for 0.5-24 h; (2) adding 1-1000 μL of silica sol into the step (1) under stirring at 25-100 ℃ for 0.5-24 h; then adding a precipitant solution with a mass concentration of 1-40% under stirring, and adding 1-100 g of ammonium molybdate into the mixture under stirring at 25-100 ℃ for 0.5-24 h; (3) filtering and drying, and then reducing in a tube furnace under a hydrogen atmosphere at 300-700 ℃ for 1-24 h to obtain the Ni-Mo supported diatomite catalyst; The molar ratio of the precipitant solution to the nickel salt solution is 1-5:

1.

2. Use according to claim 1, characterized in that: The nickel salt solution is a solution of one or more of nickel nitrate, nickel sulfate, nickel chloride or nickel acetate.

3. Use according to claim 1, characterized in that: The precipitant solution is a solution of one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate, ammonia water or urea.

4. Use according to claim 1, characterized in that, The preparation process of THDCPD petroleum resin by hydrogenation of DCPD petroleum resin is as follows: The catalyst is reacted with DCPD petroleum resin in a solvent for 1-10 h; the reaction temperature is 220-260 ℃, the hydrogen pressure is 5-7 MPa, and the reaction device is a kettle type reactor, a loop reactor or a fixed bed reactor.

5. Use according to claim 4, characterized in that, The mass ratio of the catalyst to DCPD petroleum resin is 0.02-0.6:

1.

6. Use according to claim 4, characterized in that: The solvent is one or more of decalin, tetrahydrofuran, dioxane, petroleum ether, solvent oil, cyclohexane, methylcyclohexane and n-heptane.

7. Use according to claim 4, characterized in that: The mass ratio of the solvent to DCPD petroleum resin is 1:1-20:1.

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