High-loading-capacity nickel-based catalyst for C5 petroleum resin hydrogenation and preparation method of high-loading-capacity nickel-based catalyst

Abstract

The invention belongs to the field of catalyst preparation technology and application, and relates to a preparation method of a nickel-based catalyst for C5 petroleum resin hydrogenation, and the nickel-based catalyst comprises a self-made carrier, an active component Ni and an oxide auxiliary agent. In the catalyst, the ratio of the carrier is 60-75%, the ratio of the active component metal Ni is 20-35%, and the ratio of the oxide auxiliary agent is 2-5%. The C5 petroleum resin hydrogenation reaction is carried out by using the catalyst provided by the invention, the hydrogenated C5 petroleum resin has a lower yellow index and a higher product conversion rate, and the effect of the C5 petroleum resin hydrogenation reaction is superior to the effect of using a commercial catalyst.

Description

Technical Field

[0001] The invention belongs to the technical field of catalyst materials, and in particular relates to a preparation method and application of a nickel-based catalyst for hydrogenation of C5 petroleum resin. Background Art

[0002] C5 petroleum resin is a functional resin polymerized with cracked C5 fraction as the main raw material under the action of Friedel Crafts catalyst. The cracked C5 fraction is mainly a by-product of ethylene produced by steam cracking of naphtha or other heavy cracked raw materials. With the continuous development of my country's petrochemical industry, the ethylene production capacity has increased year by year, which has also promoted the rapid development of my country's C5 petroleum resin industry. The average relative molecular weight of C5 petroleum resin is between 1000 and 3000, and its appearance is yellow or light brown. The resin is inexpensive and has excellent properties such as acid and alkali resistance, weather resistance, aging resistance, and good adhesion. It is widely used in coatings, inks, seals, adhesives, etc. With the in-depth advancement of technology, the use requirements and quality of resins in various industries have been further improved. There are still many unsaturated bonds and impurities in the structure of ordinary C5 petroleum resin, and there are problems such as deep color, odor, poor oxidation resistance, and poor thermal stability.

[0003] C5 petroleum resin hydrogenation modification is to introduce hydrogen into the mixture of resin and solvent during the production process for hydrogenation reaction. Catalytic hydrogenation saturates the double bonds in C5 petroleum resin and removes impurities remaining in the resin production process, thus forming C5 hydrogenated petroleum resin. C5 hydrogenated petroleum resin has good chromaticity, thermal stability and chemical stability, which greatly broadens its application market.

[0004] At present, the commonly used C5 petroleum resin hydrogenation catalysts in China are mainly divided into two categories, precious metal catalysts and non-precious metal catalysts. Precious metal catalysts such as Pd, Pt, and Ru-based catalysts have the characteristics of high reaction activity and low reaction temperature, but the cost of precious metals is relatively high, and they are easily affected by impurities such as S and Cl in the raw materials, resulting in catalyst deactivation. Non-precious metal catalysts are mainly nickel-based catalysts, which are widely used because of their advantages such as low price, good dispersibility, and strong stability.

[0005] Chinese patent application document CN102935370A discloses a preparation method of loading Ni / Mg / Cu on an alumina-titania composite carrier, CN106268824A discloses a nickel-based catalyst loaded on diatomaceous earth treated with a pore-expanding agent, and CN112705227A discloses a method of preparing a nickel-based catalyst using a Mo and W modified porous oxide carrier, etc. Many data show that the preparation process of nickel-based catalysts is complex and diverse, and a key point is the preparation and treatment of the carrier, which is closely related to the problems of complex process, low activity, and harsh reaction conditions that nickel-based catalysts always have. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a preparation method and application of a high-load nickel-based catalyst in view of the deficiencies of the above-mentioned prior art. The nickel-based catalyst is composed of a self-made carrier, an active component Ni and an auxiliary agent, and the catalyst metal is loaded by a step-by-step impregnation method. The above-mentioned catalyst of the present invention is used for the hydrogenation reaction of C5 petroleum resin, and the hydrogenation performance is better than that of commercial catalysts. The hydrogenated C5 petroleum resin has a lower yellow index and a higher product conversion rate.

[0007] On the one hand, the present invention provides a high-load nickel-based catalyst, which includes a carrier, an active component Ni and an oxide additive; based on the mass fraction of the catalyst, the active component metal Ni accounts for 20-35%, the carrier accounts for 60-75%, and the oxide additive accounts for 2-5%.

[0008] Preferably, in the nickel-based catalyst, the carrier source is silica sol and aluminum sol, the mass fraction of silicon oxide / aluminum oxide in the sol is 30%wt; the source of the active component metal Ni is selected from one or more of nickel formate, nickel acetate or nickel oxalate, and the auxiliary agent is CeO2.

[0009] Furthermore, the catalyst has the following properties: specific surface area of ​​150 to 300 m 2 / g, pore volume 0.2~0.5cm 3 / g, pore size is 5~8nm.

[0010] Another aspect of the present invention provides a method for preparing the above-mentioned high-load nickel-based catalyst, which includes carrier preparation, metal loading, calcination and reduction processes, specifically comprising the following steps:

[0011] Step 1: Add a certain amount of silica sol and aluminum sol into a stirring tank, add an appropriate amount of pure water to dilute, and stir for 60 minutes in a water bath at 40-60° C. to form a silica-aluminum mixed sol.

[0012] Step 2: prepare a certain mass fraction of weak alkaline ammonium salt solution, slowly drip it into the stirring tank in step 1, adjust the pH to 6-8, add a small amount of pore-forming agent, continue stirring for 2 hours, and obtain a silicon-aluminum mixed gel; place the above gel in an oven at 100-120°C for further aging for 6-8 hours, and obtain a powdered carrier after drying, grinding and calcining.

[0013] Step three, place the powdered carrier obtained in step two, a small amount of auxiliary agent CeO2 and a stabilizer in a stirring tank, add water and mix evenly; weigh a certain amount of nickel salt, add water to prepare a solution, add it to the above system, and perform excess volume impregnation. After sufficient impregnation for a period of time, filter and collect the filtrate, place the filter cake in an oven at 100-120°C for drying, and obtain the catalyst precursor a after calcination.

[0014] Step 4: Take the filtrate obtained in step 3 and mix it evenly with the catalyst precursor a, heat and stir, slowly evaporate the water, and after the impregnation is completed, dry and calcine to obtain the catalyst precursor b.

[0015] Step 5, subjecting the catalyst precursor b obtained in the above step 4 to high-temperature hydrogen reduction; after cooling to room temperature, performing surface passivation treatment under the protection of inert gas N2 to obtain the final high-load nickel-based catalyst.

[0016] Preferably, the mass ratio of the silica sol to the aluminum sol in step 1 is mSiO2:mAl2O3=5-10:1;

[0017] Preferably, the weakly alkaline ammonium salt solution described in step 2 is selected from one or more of ammonium carbonate, ammonium bicarbonate, and urea, and its mass fraction is 3% to 5%; the pore-forming agent described in step 2 is selected from one or more of polymethacrylate, polyvinyl alcohol, and polyvinyl pyrrolidone, and its amount is 0.5% to 1% of the mass of the catalyst; the calcination conditions described in step 2 are calcination at 500 to 550° C. in an air atmosphere.

[0018] Preferably, the stabilizer described in step three is selected from one or more of zinc stearate, magnesium stearate, and calcium stearate, and its amount is 0.5% to 1% of the mass of the catalyst; the nickel salt described in step three is selected from one or more of nickel formate, nickel acetate or nickel oxalate; the calcination temperature described in step three is 500 to 550° C.; the drying and calcination conditions described in step four are the same as those in step three.

[0019] Preferably, the high temperature reduction condition in step five is 400-500° C., and the time is 4-8 hours; the surface passivation treatment in step five is CO2-O2 mixed gas passivation, and the passivation time is 8-10 hours.

[0020] Furthermore, the present invention also provides an application of the aforementioned high-loaded nickel-based catalyst in catalyzing the hydrogenation reaction of C5 petroleum resin.

[0021] Beneficial Effects of the Invention

[0022] (1) The supported catalyst of the present invention is prepared by an impregnation process. The step-by-step impregnation can obtain a high-load, uniform and stable nickel-based catalyst. The catalyst pores are not easily blocked and the metal is not easily detached. In the catalytic C5 petroleum resin hydrogenation reaction, the reaction activity and selectivity are better than those of commercial catalysts.

[0023] (2) The supported catalyst described in the present invention is prepared by combining an inorganic pore-forming agent (ammonium salt) with an organic pore-forming agent. The supported catalyst has the characteristics of large pore size, moderate pore volume, large specific surface area, uniform particle size distribution, good dispersibility and filterability.

[0024] (3) The supported catalyst described in the present invention selects short-chain organic nickel salt as raw material, so that its small molecules are more easily adsorbed onto the surface of the porous carrier, thereby increasing the loading amount and dispersibility of nickel metal; and nickel oxide can be obtained by simple roasting treatment. Compared with the preparation using conventional inorganic acid salts (such as nickel chloride, nickel nitrate, nickel sulfate, etc.), this method does not require a large amount of pure water washing to remove acid ions, and no pollutants are generated.

[0025] (4) The supported catalyst of the present invention introduces CeO2 as an oxide promoter, which can improve the stability of the catalyst. The activity does not decay during multiple uses, and the color and thermal stability of the hydrogenated petroleum resin are effectively improved. DETAILED DESCRIPTION

[0026] For a better understanding of the present invention, the present invention is illustrated by the following examples. It should be clear to those skilled in the art that the examples are only to help understand the present invention and should not be regarded as specific limitations of the present invention. The raw materials involved in the embodiments of the present invention, unless otherwise specified, can be obtained from commercial sources or synthesized using commercially available starting materials and reagents by conventional methods in the art.

[0027] Example 1

[0028] This embodiment provides a high-load nickel-based catalyst A, which includes a carrier, an active component Ni and an oxide additive; based on the mass fraction of the catalyst, the active component metal Ni accounts for 20%, the carrier accounts for 75%, and the oxide additive accounts for 5%.

[0029] The preparation method of high-load nickel-based catalyst A is as follows: step 1, adding 41.67 g silica sol and 8.33 g aluminum sol into a stirring kettle, adding 200 mL pure water to dilute, and stirring for 60 min in a 60° C. water bath to form a silica-aluminum mixed sol;

[0030] Step 2: prepare a 5% ammonium carbonate solution by mass, slowly drip it into the stirring kettle in step 1, adjust the pH to 6.0, add 0.10g polymethyl methacrylate, and continue stirring for 2 hours to obtain a silicon-aluminum mixed gel; place the above gel in a 120°C oven and continue aging for 6 hours, dry, grind, and place it in a muffle furnace at 500°C in an air atmosphere to obtain a powdered carrier.

[0031] Step 3, the powdered carrier obtained in step 2, 1.00g CeO2 and 0.14g magnesium stearate are placed in a stirring kettle and 50ml water is added to mix evenly; 16.96g nickel acetate tetrahydrate is weighed and 60ml pure water is added to prepare a solution, which is added to the above system for excess volume impregnation. After fully impregnating for 1h, the filtrate is collected by filtration, and the filter cake is placed in an oven at 120°C for drying, and calcined at 550°C in an air atmosphere for 4h to obtain a catalyst precursor a;

[0032] Step 4: Take the filtrate obtained in step 3 and mix it evenly with catalyst precursor a, stir while heating, and slowly evaporate the water. After the impregnation is completed, place the solid in an oven at 120°C for drying and calcine at 550°C in air atmosphere for 4 hours to obtain catalyst precursor b.

[0033] Step 5: The catalyst precursor b obtained in the above step 4 is reduced at 450° C. in a hydrogen atmosphere for 6 h. After cooling to room temperature, a CO2-O2 mixed gas is slowly introduced under the protection of an inert gas N2 for passivation for 10 h to obtain the final high-load nickel-based catalyst A.

[0034] Example 2

[0035] This embodiment provides a high-load nickel-based catalyst B, which includes a carrier, an active component Ni and an oxide additive; based on the mass fraction of the catalyst, the active component metal Ni accounts for 25%, the carrier accounts for 72%, and the oxide additive accounts for 3%.

[0036] The preparation method of high-load nickel-based catalyst B is as follows: step 1, adding 42.00 g silica sol and 6.00 g aluminum sol into a stirring kettle, adding 200 mL pure water to dilute, and stirring for 60 min in a 40° C. water bath to form a silica-aluminum mixed sol;

[0037] Step 2: prepare a 3% ammonium bicarbonate solution, slowly drip it into the stirring kettle in step 1, adjust the pH to 6.5, add 0.20g polyvinyl pyrrolidone, and continue stirring for 2 hours to obtain a silicon-aluminum mixed gel; place the above gel in a 100°C oven for further aging for 8 hours, dry, grind, and place it in a muffle furnace at 550°C in an air atmosphere for 6 hours to obtain a powdered carrier.

[0038] Step 3, the powdered carrier obtained in step 2, 0.60g CeO2 and 0.12g zinc stearate are placed in a stirring kettle and 50ml water is added to mix evenly; 21.20g nickel acetate tetrahydrate is weighed and 60mL pure water is added to prepare a solution, which is added to the above system for excess volume impregnation. After sufficient impregnation for 1h, the filtrate is collected by filtration, and the filter cake is placed in an oven at 120°C for drying and calcined at 500°C in air atmosphere for 6h to obtain catalyst precursor a;

[0039] Step 4: Take the filtrate obtained in step 3 and mix it evenly with catalyst precursor a, stir while heating, and slowly evaporate the water. After the impregnation is completed, place the solid in an oven at 120°C for drying and calcine in an air atmosphere at 500°C for 6 hours to obtain catalyst precursor b.

[0040] Step 5: The catalyst precursor b obtained in the above step 4 is reduced in a hydrogen atmosphere at 400°C for 8 hours. After cooling to room temperature, a CO2-O2 mixed gas is slowly introduced under the protection of an inert gas N2 for passivation for 8 hours to obtain the final high-load nickel-based catalyst B.

[0041] Example 3

[0042] This embodiment provides a high-load nickel-based catalyst C, which includes a carrier, an active component Ni and an oxide additive; based on the mass fraction of the catalyst, the active component metal Ni accounts for 27%, the carrier accounts for 70%, and the oxide additive accounts for 3%.

[0043] The preparation method of high-load nickel-based catalyst C is as follows: step 1, adding 40.00 g silica sol and 6.67 g aluminum sol into a stirring kettle, adding 200 mL pure water to dilute, and stirring for 60 min in a 60° C. water bath to form a silica-aluminum mixed sol;

[0044] Step 2: prepare a 3% urea solution by mass, slowly drip it into the stirring kettle in step 1, adjust the pH to 6.8, add 0.12g of polyvinyl pyrrolidone, and continue stirring for 2 hours to obtain a silicon-aluminum mixed gel; place the above gel in a 100°C oven for further aging for 8 hours, dry, grind, and place it in a muffle furnace at 550°C in an air atmosphere for 4 hours to obtain a powdered carrier.

[0045] Step 3, the powdered carrier obtained in step 2, 0.60g CeO2 and 0.10g calcium stearate are placed in a stirring kettle and 50ml water is added to mix evenly; 17.00g nickel formate dihydrate is weighed and 60ml pure water is added to prepare a solution, which is added to the above system for excess volume impregnation. After fully impregnating for 1h, the filtrate is collected by filtration, and the filter cake is placed in an oven at 100°C for drying and calcined at 500°C in air atmosphere for 6h to obtain catalyst precursor a;

[0046] Step 4: Take the filtrate obtained in step 3 and mix it evenly with catalyst precursor a, stir while heating, and slowly evaporate the water. After the impregnation is completed, place the solid in an oven at 100°C for drying and calcine in an air atmosphere at 500°C for 6 hours to obtain catalyst precursor b.

[0047] Step 5: The catalyst precursor b obtained in step 4 is reduced in a hydrogen atmosphere at 500°C for 4 hours. After cooling to room temperature, a CO2-O2 mixed gas is slowly introduced under the protection of an inert gas N2 for passivation for 10 hours to obtain the final high-load nickel-based catalyst C.

[0048] Example 4

[0049] This embodiment provides a high-load nickel-based catalyst D, which includes a carrier, an active component Ni and an oxide additive; based on the mass fraction of the catalyst, the active component metal Ni accounts for 30%, the carrier accounts for 68%, and the oxide additive accounts for 2%.

[0050] The preparation method of high-load nickel-based catalyst D is as follows: step 1, adding 41.20 g silica sol and 6.67 g aluminum sol into a stirring kettle, adding 200 mL pure water to dilute, and stirring for 60 min in a 60° C. water bath to form a silica-aluminum mixed sol;

[0051] Step 2: prepare a 5% urea solution by mass, slowly drip it into the stirring tank in step 1, adjust the pH to 7.0, add 0.20g polyvinyl alcohol, continue stirring for 2 hours, and obtain a silicon-aluminum mixed gel; place the above gel in a 120°C oven and continue aging for 6 hours, dry, grind, and place it in a muffle furnace at 550°C in an air atmosphere for 4 hours to obtain a powdered carrier.

[0052] Step 3, the powdered carrier obtained in step 2, 0.40g CeO2 and 0.20g calcium stearate are placed in a stirring kettle and 50ml water is added to mix evenly; 18.89g nickel formate dihydrate is weighed and 60ml pure water is added to prepare a solution, which is added to the above system for excess volume impregnation. After fully impregnating for 1h, the filtrate is collected by filtration, and the filter cake is placed in an oven at 120°C for drying and calcined in an air atmosphere at 500°C for 4h to obtain a catalyst precursor a;

[0053] Step 4: Take the filtrate obtained in step 3 and mix it evenly with catalyst precursor a, stir while heating, and slowly evaporate the water. After the impregnation is completed, place the solid in an oven at 120°C for drying and calcine in an air atmosphere at 500°C for 4 hours to obtain catalyst precursor b.

[0054] Step 5: The catalyst precursor b obtained in the above step 4 is reduced at 450° C. in a hydrogen atmosphere for 6 h. After cooling to room temperature, a CO2-O2 mixed gas is slowly introduced under the protection of an inert gas N2 for passivation for 10 h to obtain the final high-load nickel-based catalyst D.

[0055] Example 5

[0056] This embodiment provides a high-load nickel-based catalyst E, which includes a carrier, an active component Ni and an oxide additive; based on the mass fraction of the catalyst, the active component metal Ni accounts for 32%, the carrier accounts for 65%, and the oxide additive accounts for 3%.

[0057] The preparation method of high-load nickel-based catalyst E is as follows: step 1, adding 37.92 g silica sol and 4.74 g aluminum sol into a stirring kettle, adding 200 mL pure water to dilute, and stirring for 60 min in a 45° C. water bath to form a silica-aluminum mixed sol;

[0058] Step 2: prepare a 4% ammonium bicarbonate solution, slowly drip it into the stirring kettle in step 1, adjust the pH to 7.5, add 0.15g polyvinyl alcohol, and continue stirring for 2 hours to obtain a silicon-aluminum mixed gel; place the above gel in a 120°C oven and continue aging for 6 hours, dry, grind, and place it in a muffle furnace at 500°C in an air atmosphere for 6 hours to obtain a powdered carrier.

[0059] Step 3, the powdered carrier obtained in step 2, 0.60g CeO2 and 0.12g zinc stearate are placed in a stirring kettle, 50ml water is added and mixed evenly; 19.93g nickel oxalate dihydrate is weighed and 60ml pure water is added to prepare a solution, which is added to the above system for excess volume impregnation. After sufficient impregnation for 1h, the filtrate is collected by filtration, the filter cake is placed in an oven at 120°C for drying, and calcined in an air atmosphere at 500°C for 6h to obtain a catalyst precursor a;

[0060] Step 4: Take the filtrate obtained in step 3 and mix it evenly with catalyst precursor a, stir while heating, and slowly evaporate the water. After the impregnation is completed, place the solid in an oven at 120°C for drying and calcine in an air atmosphere at 500°C for 6 hours to obtain catalyst precursor b.

[0061] Step 5: The catalyst precursor b obtained in the above step 4 is reduced at 450° C. in a hydrogen atmosphere for 8 h. After cooling to room temperature, a CO2-O2 mixed gas is slowly introduced under the protection of an inert gas N2 for passivation for 10 h to obtain the final high-load nickel-based catalyst E.

[0062] Example 6

[0063] This embodiment provides a high-load nickel-based catalyst F, which includes a carrier, an active component Ni and an oxide additive; based on the mass fraction of the catalyst, the active component metal Ni accounts for 35%, the carrier accounts for 60%, and the oxide additive accounts for 5%.

[0064] The preparation method of high-load nickel-based catalyst F is as follows: step 1, adding 36.00 g silica sol and 4.00 g aluminum sol into a stirring kettle, adding 200 mL pure water to dilute, stirring for 60 min in a 60° C. water bath to form a silica-aluminum mixed sol;

[0065] Step 2: prepare a 5% ammonium carbonate solution by mass, slowly drip it into the stirring kettle in step 1, adjust the pH to 8.0, add 0.10g polymethyl methacrylate, and continue stirring for 2 hours to obtain a silicon-aluminum mixed gel; place the above gel in a 120°C oven and continue aging for 6 hours, dry, grind, and place it in a muffle furnace at 550°C in an air atmosphere for 4 hours to obtain a powdered carrier.

[0066] Step 3, the powdered carrier obtained in step 2, 1.00g CeO2 and 0.15g magnesium stearate are placed in a stirring kettle, 50ml water is added and mixed evenly; 21.80g nickel oxalate dihydrate is weighed and 60ml pure water is added to prepare a solution, which is added to the above system for excess volume impregnation. After fully impregnating for 1h, the filtrate is collected by filtration, the filter cake is placed in an oven at 120°C for drying, and calcined at 550°C in air atmosphere for 4h to obtain catalyst precursor a;

[0067] Step 4: Take the filtrate obtained in step 3 and mix it evenly with catalyst precursor a, stir while heating, and slowly evaporate the water. After the impregnation is completed, place the solid in an oven at 120°C for drying and calcine at 550°C in air atmosphere for 4 hours to obtain catalyst precursor b.

[0068] Step 5: The catalyst precursor b obtained in the above step 4 is reduced in a hydrogen atmosphere at 400° C. for 8 h. After cooling to room temperature, a CO2-O2 mixed gas is slowly introduced under the protection of an inert gas N2 for passivation for 10 h to obtain the final high-load nickel-based catalyst F.

[0069] Example 7

[0070] This embodiment provides a high-load nickel-based catalyst G, which includes a carrier, an active component Ni and an oxide additive; based on the mass fraction of the catalyst, the active component metal Ni accounts for 25%, the carrier accounts for 75%, and the oxide additive accounts for 0%.

[0071] The preparation method of high-load nickel-based catalyst G is as follows: step 1, adding 42.86 g silica sol and 6.12 g aluminum sol into a stirring kettle, adding 200 mL pure water to dilute, and stirring for 60 min in a 40° C. water bath to form a silica-aluminum mixed sol;

[0072] Step 2: prepare a 3% ammonium bicarbonate solution, slowly drip it into the stirring kettle in step 1, adjust the pH to 6.5, add 0.20g polyvinyl pyrrolidone, and continue stirring for 2 hours to obtain a silicon-aluminum mixed gel; place the above gel in a 100°C oven for further aging for 8 hours, dry, grind, and place it in a muffle furnace at 550°C in an air atmosphere for 6 hours to obtain a powdered carrier.

[0073] Step 3, the powdered carrier obtained in step 2 and 0.12g of zinc stearate are placed in a stirring kettle and 50ml of water are added to mix evenly; 21.20g of nickel acetate tetrahydrate is weighed and 60ml of pure water is added to prepare a solution, which is added to the above system for excess volume impregnation. After sufficient impregnation for 1h, the filtrate is collected by filtration, and the filter cake is placed in an oven at 120°C for drying and calcined in an air atmosphere at 500°C for 6h to obtain a catalyst precursor a;

[0074] Step 4: Take the filtrate obtained in step 3 and mix it evenly with catalyst precursor a, stir while heating, and slowly evaporate the water. After the impregnation is completed, place the solid in an oven at 120°C for drying and calcine in an air atmosphere at 500°C for 6 hours to obtain catalyst precursor b.

[0075] Step 5: The catalyst precursor b obtained in the above step 4 is reduced in a hydrogen atmosphere at 400°C for 8 hours. After cooling to room temperature, a CO2-O2 mixed gas is slowly introduced under the protection of an inert gas N2 for passivation for 8 hours to obtain the final high-load nickel-based catalyst G.

[0076] Evaluation of Hydrogenation Performance of C5 Petroleum Resin

[0077] The test method for evaluating the hydrogenation performance of C5 petroleum resin of the catalysts (A-G) of Examples 1-7 is as follows: 50g of C5 petroleum resin is dissolved in 100g of solvent oil, 1g of catalyst is added, and the mixture is transferred to a 500mL high-pressure reactor, and the temperature is raised and stirred at 500rpm. The temperature is raised to about 180°C to replace the air in the reactor, and hydrogen is introduced to start the hydrogenation reaction. The reaction pressure is 7Mpa, the reaction temperature is 220°C, and the reaction time is 3h. After the reaction, the reaction liquid is separated from the catalyst, and the yellowness index (YI) of the white solid is measured after the solvent is removed from the reaction liquid. The index is tested using a HunterLab UltraScan VIS instrument; the catalyst is recovered after separation and continues to be applied. The comparison sample is a commercial carrier nickel catalyst of BASF, model Ni-5249P.

[0078] The evaluation results of the hydrogenation performance of catalysts A to G are shown in the following table:

[0079]

[0080] It can be seen from the above experimental results that in the hydrogenation reaction of C5 petroleum resin, the catalysts (A to G) of the present invention are more effective and show hydrogenation performance superior to that of commercial catalysts. The hydrogenated C5 petroleum resin has a lower yellowness index and a higher product conversion rate.

[0081] For any technician familiar with the art, without departing from the scope of the technical solution of the present invention, the technical content disclosed above can be used to make many possible changes and modifications to the technical solution of the present invention, or modified into equivalent embodiments with equivalent changes. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention should still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A high-load nickel-based catalyst for hydrogenation of C5 petroleum resin, characterized in that: The nickel-based catalyst comprises a carrier, an active component metal Ni and an oxide additive; based on the mass fraction of the catalyst, the active component metal Ni accounts for 20-35%, the carrier accounts for 60-75%, and the oxide additive accounts for 2-5%; The carrier is silica sol and aluminum sol, the mass fraction of silicon oxide / aluminum oxide in the sol is 30%; the oxide auxiliary agent is CeO2; the source of the active component metal Ni is selected from one or more of nickel formate, nickel acetate and nickel oxalate.

2. The high-load nickel-based catalyst according to claim 1, characterized in that The specific surface area of ​​the catalyst is 150 to 300 m 2 / g, pore volume is 0.2~0.5cm 3 / g, pore size is 5~8nm.

3. The method for preparing a high-load nickel-based catalyst according to claim 1 or 2, characterized in that: Including carrier preparation, metal loading, calcination and reduction process, the specific steps are: Step 1: Add a certain amount of silica sol and aluminum sol into a stirring kettle, add an appropriate amount of pure water to dilute, and stir for 60 minutes in a water bath at 40-60°C to form a silica-aluminum mixed sol; Step 2: prepare a certain mass fraction of weak alkaline ammonium salt solution, slowly drip it into the stirring kettle in step 1, adjust the pH to 6-8, add a small amount of pore-forming agent, continue stirring for 2 hours, and obtain a silicon-aluminum mixed gel; place the above gel in an oven at 100-120°C for further aging for 6-8 hours, and obtain a powdered carrier after drying, grinding and calcining; Step 3, placing the powdered carrier obtained in step 2, a small amount of auxiliary agent CeO2 and a stabilizer in a stirring tank, adding water and mixing evenly; weighing a certain amount of nickel salt, adding water to prepare a solution, adding it to the above system, and performing excess volume impregnation. After sufficient impregnation for a period of time, filtering and collecting the filtrate, placing the filter cake in an oven at 100-120°C for drying, and obtaining the catalyst precursor a after calcination; Step 4: Take the filtrate obtained in step 3 and mix it evenly with the catalyst precursor a, heat and stir, slowly evaporate the water, and after the impregnation is completed, dry and calcine to obtain the catalyst precursor b; Step 5: subjecting the catalyst precursor b obtained in the above step 4 to high-temperature hydrogen reduction; after cooling to room temperature, subjecting the catalyst precursor b to surface passivation treatment under the protection of inert gas N2 to obtain the final high-load nickel-based catalyst.

4. The method for preparing a high-load nickel-based catalyst according to claim 3, characterized in that: The mass ratio of the silica sol to the aluminum sol described in step 1 is mSiO2:mAl2O3=5~10:

1.

5. The method for preparing a high-load nickel-based catalyst according to claim 3, characterized in that: The weakly alkaline ammonium salt solution described in step 2 is selected from one or more of ammonium carbonate, ammonium bicarbonate, and urea, with a mass fraction of 3% to 5%.

6. The method for preparing a high-load nickel-based catalyst according to claim 3, characterized in that: The pore-forming agent described in step 2 is selected from one or more of polymethacrylate, polyvinyl alcohol, and polyvinyl pyrrolidone, and the amount of the pore-forming agent is 0.5% to 1% of the catalyst mass; the calcination conditions described in step 2 are calcination at 500 to 550° C. in an air atmosphere.

7. The method for preparing a high-load nickel-based catalyst according to claim 3, characterized in that: The stabilizer described in step three is selected from one or more of zinc stearate, magnesium stearate, and calcium stearate, and the amount of the stabilizer is 0.5% to 1% of the mass of the catalyst; the calcination temperature described in steps three and four is 500 to 550°C.

8. The method for preparing a high-load nickel-based catalyst according to claim 3, characterized in that: The high temperature reduction condition described in step five is 400-500° C., and the time is 4-8 hours; the surface passivation treatment described in step five is CO2-O2 mixed gas passivation, and the passivation time is 8-10 hours.

9. Use of the high-loaded nickel-based catalyst according to any one of claims 1 to 2 or the high-loaded nickel-based catalyst obtained by the preparation method according to any one of claims 3 to 8, characterized in that: The high-loaded nickel-based catalyst is used as a catalyst in catalyzing the hydrogenation reaction of C5 petroleum resin.

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