Petroleum resin hydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention discloses a petroleum resin hydrogenation catalyst and a preparation method and application thereof. The petroleum resin hydrogenation catalyst is of a spherical core-shell structure and comprises active metal components and a carrier, the active metal components are nickel oxide and zinc oxide, and the carrier is aluminum oxide. The invention also provides a preparation method of the petroleum resin hydrogenation catalyst and application of the petroleum resin hydrogenation catalyst in a petroleum resin hydrotreating process. By optimizing and adjusting the pore structure of the catalyst and the distribution of the active metal, the double functions of hydrodesulfurization on the upper shell layer of the catalyst and hydrogenation decolorization on the core layer of the catalyst are realized. Meanwhile, the catalyst has the advantages of high sulfur tolerance, hydrogenation decolorization performance and stability, and is especially suitable for the hydrotreating process of C5 and C9 petroleum resin.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of petrochemical industry, and relates to a catalytic material and a preparation method thereof, in particular to a petroleum resin catalyst and a preparation method and application thereof. BACKGROUND

[0002] The petroleum resin is a functional resin with relatively low molecular weight, and has the properties of tackiness, adhesion and compatibility with other resins. It is widely used in the fields of coatings, adhesives, printing inks, rubber additives, paper additives and the like. The petroleum resin can be divided into C5 petroleum resin, C9 petroleum resin and C5-C9 copolymer petroleum resin according to different production raw materials and properties. At present, the petroleum resin is mainly derived from the by-products of petroleum cracking ethylene, and has the problems of deep color, poor thermal stability and oxidation stability, especially the existence of double bonds and benzene rings seriously affects the color, stability and compatibility with other resins, thereby limiting the application range.

[0003] The petroleum resin can be modified to expand the application range. Hydrogenation treatment of the petroleum resin is one of important means for modifying the petroleum resin, that is, the double bonds and part of the benzene rings in the petroleum resin molecules are hydrogenated and saturated under the condition of hydrogen and catalyst, and the halogen elements remaining in the petroleum resin during polymerization can also be removed, so as to improve the color, light and thermal stability of the petroleum resin, improve the product quality, and expand the application range of the petroleum resin. The selling price of the petroleum resin after hydrogenation modification can be increased by about one time. It can be seen that the hydrogenation modified petroleum resin not only has great industrial application significance, but also has broad commercial prospects.

[0004] The petroleum resin hydrogenation catalyst is the core of the whole technology, which determines the production cost and the quality of the subsequent product. At present, the petroleum resin hydrogenation catalysts are mainly divided into two categories: noble metal type and non-noble metal type, and most of them are supported catalysts. The noble metal catalysts are mainly platinum and palladium catalysts, which have strong olefin and aromatic hydrocarbon saturation capacity, and can achieve ideal effect in the hydrogenation decolorization of the petroleum resin. The non-noble metal catalysts are mainly nickel catalysts, which can cause slight degradation of the resin during hydrogenation, and appropriate hydrogenation cracking can improve the mutual solubility of the resin.

[0005] Although the noble metal catalyst can effectively limit the cracking side reaction of the resin hydrogenation, it also has the following disadvantages: first, the preparation cost of the noble metal catalyst is much higher than that of the non-noble metal catalyst; second, the noble metal catalyst has strict requirements for the impurity content in the raw material, especially the sulfur content in the raw material. Therefore, when the noble metal catalyst is used, a protective catalyst is generally added before the main catalyst to solve the above problems through catalyst grading.

[0006] Patent CN117920208A discloses a C5 petroleum resin hydrogenation catalyst and its preparation method and application. The C5 petroleum resin hydrogenation catalyst includes a modified alumina carrier and an active metal component, wherein the modified alumina carrier is an ordered mesoporous alumina carrier with a surface modified by a carrier additive, and the carrier additive is at least one of CeO2, TiO2 and La2O3. The catalyst is used in C5 petroleum resin hydrogenation reaction and has high activity and stability. However, the sulfur resistance of the catalyst is not improved, and a finishing catalyst is still needed to protect the main catalyst.

[0007] Patent CN111574645A discloses a method for hydrogenation of high-sulfur petroleum resin, belonging to the technical field of polymer hydrogenation. A supported bimetallic alloy catalyst is used as a pre-hydrogenation desulfurization catalyst, and a supported metal catalyst is used as a hydrogenation decolorization catalyst. The resin is subjected to hydrogenation reaction in a two-stage fixed-bed continuous hydrogenation mode. The obtained hydrogenated resin has improved color and good thermal stability. This patent also uses catalyst grading to achieve hydrogenation of high-sulfur resin, and the use of a bimetallic alloy desulfurization catalyst is not conducive to popularization. SUMMARY

[0008] In order to overcome the deficiencies in the prior art, the main purpose of the present application is to provide a petroleum resin hydrogenation catalyst and its preparation method and application. The catalyst has a spherical core-shell structure. By optimizing and adjusting the pore structure and active metal distribution of the catalyst, a dual function of hydrogenation desulfurization in the shell layer and hydrogenation decolorization in the core layer is achieved. The petroleum resin hydrogenation catalyst provided by the present application has the advantages of strong sulfur resistance, high hydrogenation decolorization performance and stability, and is especially suitable for C5 and C9 petroleum resin hydrogenation treatment processes.

[0009] The first aspect of the present application provides a preparation method of a petroleum resin hydrogenation catalyst, comprising the following steps:

[0010] (1) Under mixing conditions, the pseudoboehmite and the aqueous solution of the organic high polymer after heat treatment are uniformly mixed, and after spherical molding treatment, a carrier precursor A is obtained;

[0011] (2) After drying and calcination treatment of the carrier precursor A, a carrier A is obtained;

[0012] (3) Under mixing conditions, the organic high polymer, weakly basic compound and pseudoboehmite are uniformly mixed to prepare material B;

[0013] (4) The carrier A is put into a rolling machine, and the material B obtained in step (3) and the aqueous solution of the organic high polymer after heat treatment are added during rolling, and after treatment, a carrier precursor B is obtained;

[0014] (5) subjecting the support precursor B obtained in step (4) to heat treatment under dry conditions to obtain a support precursor C;

[0015] (6) mixing the support precursor C obtained in step (5), a nickel salt precursor and ammonia water, and drying the mixture to obtain a catalyst precursor;

[0016] (7) introducing an active metal into the catalyst precursor obtained in step (6), and then drying and calcining the same to obtain a petroleum resin hydrogenation catalyst.

[0017] Further, in the above method for preparing a petroleum resin hydrogenation catalyst, the pseudo-boehmite in step (1) has the following properties after being calcined at 600°C: a specific surface area of 290-340 m 2 / g, and a pore volume of 0.9-1.2 mL / g. The pseudo-boehmite can be a commercially available product or can be prepared according to a conventional method.

[0018] Further, in the above method for preparing a petroleum resin hydrogenation catalyst, the concentration of the aqueous solution of the heat-treated organic polymer in steps (1) and (4) is 0.5-5 wt%, preferably 1-3 wt%. The aqueous solution of the heat-treated organic polymer is prepared by adding the organic polymer to water and mixing at 60-100°C for 10-40 min, and then obtaining the aqueous solution of the heat-treated organic polymer after the organic polymer is completely dissolved.

[0019] Further, in the above method for preparing a petroleum resin hydrogenation catalyst, the mass ratio of the amount of the aqueous solution of the heat-treated organic polymer added in step (1) to the pseudo-boehmite is 0.5-1.5.

[0020] Further, in the above method for preparing a petroleum resin hydrogenation catalyst, the organic polymer in steps (1) and (3) can be one or more selected from the group consisting of starch, cellulose ether and flour, and is preferably starch. Further, the starch can be at least one selected from the group consisting of mung bean starch, cassava starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch, and is preferably corn starch and / or potato starch; and the cellulose ether can be at least one selected from the group consisting of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose and phenyl cellulose, and is preferably methyl cellulose.

[0021] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the balling and forming in step (1) can be one or more of extrusion and throwing round forming, rolling forming, and spray drying forming.

[0022] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the drying temperature in step (2) is 80-140°C, and the drying time is 3-12h.

[0023] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the calcination in step (2) is carried out in an inert atmosphere, which can be nitrogen and / or an inert gas, and the inert gas is one or more of helium, neon, argon, krypton, and xenon.

[0024] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the calcination temperature in step (2) is 500-800°C, and the calcination time is 1-5h.

[0025] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the particle size of the carrier A in step (2) is controlled to be 0.1-1.5mm, and preferably 0.2-1.2mm.

[0026] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the weakly basic compound in step (3) can be one or a mixture of two or more of aqueous ammonia, ammonium carbonate, and ammonium bicarbonate, and preferably aqueous ammonia. Further, the concentration of the aqueous ammonia is 1wt%-20wt%, and preferably 3wt%-12wt%.

[0027] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the mass ratio of the organic high molecular polymer to the weakly basic compound in step (3) is 1:0.05-1:0.5.

[0028] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the addition amount (by mass) of the organic high molecular polymer and the weakly basic compound in step (3) is 5wt%-15wt% of the dry mass of the pseudoboehmite.

[0029] Further, in the preparation method of the petroleum resin hydrogenation catalyst, in step (3), the organic high molecular polymer, the weakly basic compound, and the pseudoboehmite are mixed, and preferably the organic high molecular polymer and the weakly basic compound are mixed first, and then mixed with the pseudoboehmite.

[0030] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the pseudoboehmite in step (3) and the pseudoboehmite in step (1) can be the same or different, and preferably the same.

[0031] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the mass ratio of the heated organic polymer solution in step (4) to the pseudoboehmite in step (3) is 0.5-1.5.

[0032] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the heat treatment temperature in step (5) is 200-300℃, and the treatment time is 3-12h.

[0033] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the nickel salt precursor in step (6) is at least one of basic nickel carbonate, nickel nitrate, nickel acetate and nickel sulfate.

[0034] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the ammonia water concentration in step (6) is 10wt%-25wt%.

[0035] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the drying temperature in step (6) is 80-140℃, and the time is 3-12h.

[0036] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the active metal in step (7) is nickel and zinc.

[0037] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the introduction mode of the active metal in step (7) can be mixing the catalyst precursor with the active metal precursor and introducing by impregnation, and the active metal precursor includes a nickel salt precursor and a zinc salt precursor, the nickel salt precursor can be one or more of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride; and the zinc salt precursor can be one or more of zinc nitrate, zinc sulfate, zinc acetate and zinc chloride.

[0038] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the drying temperature in step (7) is 80-140℃, and the time is 3-12h.

[0039] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the calcination temperature in step (7) is 400-600℃, and the calcination time is 1-5h.

[0040] Further, in the preparation method of the petroleum resin hydrogenation catalyst, the catalyst particle size in step (7) is 0.3-2.0mm, and preferably 0.5-1.5mm.

[0041] The second aspect of the present application provides a petroleum resin hydrogenation catalyst prepared by the above preparation method.

[0042] Further, in the petroleum resin hydrogenation catalyst, the petroleum resin hydrogenation catalyst comprises an active metal component and a carrier, the active metal component is nickel oxide and zinc oxide, and the carrier is alumina; wherein the active metal exists in the form of oxide on the carrier.

[0043] Further, in the petroleum resin hydrogenation catalyst, the content of nickel oxide is 20wt% to 40wt% and the content of zinc oxide is 10wt% to 30wt% based on the catalyst weight.

[0044] Further, in the petroleum resin hydrogenation catalyst, the petroleum resin hydrogenation catalyst has the following properties: the specific surface area is 120m 2 / g to 220m

[0045] The third aspect of the present application provides an application of the petroleum resin hydrogenation catalyst in a petroleum resin hydrotreating process.

[0046] In the application, the petroleum resin can be C5 and / or C9 resin, further, the petroleum resin has a colority of no more than 12 (Saybolt), a softening point of no less than 110℃, and a S content of no less than 200μg / g, the petroleum resin is dissolved by a solvent before the hydrogenation reaction, and the solvent can be at least one of cyclohexane, benzene, toluene, etc.

[0047] In the application, the operating conditions of the hydrotreating process are as follows: the reaction pressure is 8MPa to 20MPa, the reaction temperature is 240℃ to 300℃, the liquid hourly space velocity is 0.3h -1 -1 to 2.0h

[0048] In the application, the petroleum resin hydrogenation catalyst needs to be reduced before use, the reduction pressure is 8MPa to 20MPa, the reduction temperature is 400℃ to 600℃, and the reduction time is 8h to 15h.

[0049] Compared with the prior art, the petroleum resin hydrogenation catalyst, the preparation method and the application thereof provided by the present application have the following advantages:

[0050] 1. The preparation method of the petroleum resin hydrogenation catalyst provided by the present application, wherein the organic high polymer is first reacted with a weak alkaline compound containing nitrogen and then mixed with pseudo-boehmite, so that the treated organic high polymer mainly plays a pore expanding role in the subsequent carrier preparation process, and the high polymer after treatment has poor adhesion; the organic high polymer aqueous solution prepared by heating has high adhesion due to the decomposition of the high polymer into small molecules in hot water, which can ensure that the pseudo-boehmite has strong interaction and can also enhance the interaction between the pseudo-boehmite and the carrier, thereby improving the strength and wear resistance of the carrier.

[0051] 2. The preparation method of the petroleum resin hydrogenation catalyst provided by the present application, wherein the organic high polymer solution after heating treatment is acidic, which is preferentially adsorbed on the basic sites of the carrier precursor A, and the carbon generated after calcination in an inert atmosphere covers the basic sites of the carrier A, so that the carrier A is acidic; when the carrier precursor B is dried, the ammonia in the weak alkaline compound containing nitrogen reacts with the organic high polymer, which is volatilized and adsorbed on the acidic sites of the outer layer of alumina, so that the outer layer of alumina is alkaline, and then the ammonia solution of nickel salt precursor is introduced, which is also alkaline and is mainly adsorbed on the inner layer of carbon-containing alumina due to the alkalinity. After drying, the ammonia is still adsorbed on the acidic sites of the outer layer of alumina, so that the outer layer of alumina continues to be alkaline, and then the active metal mixed solution is introduced, which is mainly adsorbed on the outer layer of alumina due to the acidity of the mixed solution. By using this preparation method, the inner layer active metal of the catalyst is mainly nickel oxide, and the outer layer active metal is nickel oxide and zinc oxide.

[0052] 3. The preparation method of the petroleum resin hydrogenation catalyst provided by the present application, wherein the carrier A is calcined in an inert atmosphere, and carbon is generated in situ on the acidic sites of alumina, which is beneficial to the adsorption of nickel in the impregnation process; in the later calcination in an oxygen-containing atmosphere, most of the carbon on the carrier A is burned off, only a small part of the carbon on the strong acid sites of the carrier is retained, which weakens the acidity of the inner layer of alumina carrier, and the carrier has moderate macropores, which is beneficial to the hydrogenation of macromolecular substances in the resin and avoids excessive cracking reaction.

[0053] 4. The preparation method of the petroleum resin hydrogenation catalyst provided by the present application, wherein the outer layer active metal of the catalyst is nickel oxide and zinc oxide, which mainly plays a role in hydrogenation adsorption desulfurization of the raw petroleum resin and protects the main active metal nickel in the inner layer of the catalyst; the inner layer catalyst mainly plays a role in hydrogenation decolorization of the raw material, which significantly improves the hydrogenation activity and stability of the catalyst; and the dual function of shell hydrogenation desulfurization and inner layer hydrogenation decolorization is realized in one catalyst. DETAILED DESCRIPTION

[0054] The embodiments of the present invention will be described in further detail below with reference to examples. These examples are for illustrative purposes only and should not be construed as limiting the scope of the invention.

[0055] Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "comprises" shall be understood to include the stated elements or components without excluding other elements or other components.

[0056] In this document, the terms "first," "second," etc., are used to distinguish two different elements or parts, and are not used to define specific positions or relative relationships. In other words, in some embodiments, the terms "first," "second," etc., can also be used interchangeably.

[0057] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0058] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0059] In the context of this invention, all numerical values ​​of parameters (e.g., quantity or condition) should be understood to be modified by the term “about” in all cases, regardless of whether “about” actually appears before the numerical value.

[0060] In the context of this invention, "substantially" means that deviations that are acceptable or considered reasonable to those skilled in the art are permitted, such as deviations within ±5%, ±2%, ±1%, ±0.5%, or ±0.1%.

[0061] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this instruction manual are based on weight, and the pressure is gauge pressure.

[0062] In the context of this invention, any two or more embodiments or aspects of this invention can be arbitrarily combined, and the resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of this invention.

[0063] In this invention, the specific surface area and pore volume were measured using a cryogenic liquid nitrogen physical adsorption method, specifically using a Micron ASAP2420 cryogenic nitrogen adsorption instrument. The procedure involved: a small sample was vacuum-treated at 300°C for 3–4 hours, and finally, the product was placed under cryogenic liquid nitrogen conditions (-200°C) for nitrogen adsorption-desorption testing. The surface area was obtained using the BET equation, and the pore size distribution was obtained using the BJH model.

[0064] In the context of this invention, the wear index of microsphere catalysts with a particle size less than 0.8 mm was tested using the high-speed air jet method (see ASTM D5757-00), and the wear index of microsphere catalysts with a particle size greater than 0.8 mm was measured using the drum method with a KM-ZV wear meter.

[0065] In the context of this invention, the softening point of petroleum resin is determined using GB / T 4507-2014 "Determination of Softening Point of Bituminous Pitch - Ring and Ball Method", and the color of petroleum resin is determined using the standard test method of Saybolt colorimetry for petroleum products (Saybolt colorimeter method) as specified in ASTM D156-15.

[0066] In the context of this invention, all chemical reagents and pharmaceuticals used can be obtained by purchasing commercially available products.

[0067] Example 1

[0068] (1) Catalyst preparation

[0069] Weigh 80g of corn starch and add it to 2000g of water. Heat at 90℃ for 15 minutes to obtain a heat-treated aqueous solution of organic polymer. Add 300g of boehmite (70% dry basis content, specific surface area 320m²) 2 A mixture of 160g of an aqueous solution of a heat-treated organic polymer (with a pore volume of 0.98mL / g) was homogeneous and then spheroidized to obtain carrier precursor A. This precursor was then dried at 110℃ for 8 hours and calcined at 700℃ for 2 hours under a nitrogen atmosphere to obtain carrier A. 15.8g of corn starch was first mixed with 15.0g of 10wt% ammonia solution, and then mixed with 450g of pseudoboehmite (70% dry basis content, specific surface area 320m²). 2Material B was prepared by mixing materials A (with a pore volume of 0.98 mL / g) with a pore volume of 0.98 mL / g. Support A was placed in a ball-rolling machine, and during the rolling process, material B and 240 g of an aqueous solution of a heat-treated organic polymer were added, resulting in support precursor B. Support precursor B was then heat-treated at 200 °C for 5 h to obtain support precursor C. 243 g of basic nickel carbonate was dissolved in 600 mL of a 20 wt% ammonia solution, then mixed with support precursor C, and dried at 120 °C for 8 h to obtain a catalyst precursor. 511 g of nickel nitrate and 963 g of zinc nitrate were dissolved in 600 mL of water, then added to the catalyst precursor. After standing for 2 h, the mixture was dried at 120 °C for 8 h and calcined at 500 °C for 4 h to obtain a spherical catalyst with a particle size of 0.5–0.8 mm, containing 25.0 wt% NiO and 25.0 wt% ZnO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0070] (2) Catalyst Evaluation

[0071] Cyclohexane-dissolved petroleum resin was used as raw material, with a petroleum resin mass fraction of 30%. The hydrogenation reaction was carried out in a fixed-bed tubular reactor. The reaction conditions were as follows: the reactor hydrogen pressure was increased to 15.0 MPa, the temperature was 400℃, the catalyst was reduced for 8 hours, and after the reduction was completed, the temperature was lowered to 260℃ to start the reaction again, with a volume hourly space velocity of 1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio (relative to the diluted feedstock) is 600:1. The properties of the petroleum resin are shown in Table 2, and the evaluation results are shown in Table 3.

[0072] Example 2

[0073] (1) Catalyst preparation

[0074] Weigh 100g of methylcellulose and add it to 2000g of water. Heat at 80℃ for 20min to obtain a heat-treated aqueous solution of organic polymer. Add 300g of pseudoboehmite (70% dry basis content, specific surface area 320m²) 2 A mixture of 160g of an aqueous solution of a heat-treated organic polymer (with a pore volume of 0.98mL / g) was homogeneous and then spheroidized to obtain carrier precursor A. This precursor was then dried at 110℃ for 8 hours and calcined at 650℃ for 2 hours under a nitrogen atmosphere to obtain carrier A. 52.5g of methylcellulose was first mixed with 55.0g of 15wt% ammonia solution, and then mixed with 750g of pseudoboehmite (70% dry basis content, specific surface area 320m²). 2Material B was prepared by mixing materials A (with a pore volume of 0.98 mL / g) with a pore volume of 0.98 mL / g. Support A was placed in a ball-rolling machine, and during the rolling process, material B and 720 g of a heated organic polymer aqueous solution were added to obtain support precursor B. Support precursor B was then heat-treated at 250 °C for 4 h to obtain support precursor C. 341 g of basic nickel carbonate was dissolved in 840 mL of a 20 wt% ammonia solution, then mixed with support precursor C, and dried at 120 °C for 8 h to obtain a catalyst precursor. 716 g of nickel nitrate and 1348 g of zinc nitrate were dissolved in 840 mL of water, then added to the catalyst precursor. After standing for 2 h, the mixture was dried at 120 °C for 8 h and calcined at 520 °C for 3 h to obtain a spherical catalyst with a particle size of 0.5–0.8 mm, containing 25.0 wt% NiO and 25.0 wt% ZnO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0075] (2) Catalyst Evaluation

[0076] Cyclohexane-dissolved petroleum resin was used as raw material, with a petroleum resin mass fraction of 30%. The hydrogenation reaction was carried out in a fixed-bed tubular reactor. The reaction conditions were as follows: the reactor hydrogen pressure was increased to 15.0 MPa, the temperature was 400℃, the catalyst was reduced for 8 hours, and after the reduction was completed, the temperature was lowered to 260℃ to start the reaction again, with a volume hourly space velocity of 1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio (relative to the diluted feedstock) is 600:1. The properties of the petroleum resin are shown in Table 2, and the evaluation results are shown in Table 3.

[0077] Example 3

[0078] (1) Catalyst preparation

[0079] Weigh 240g of corn starch and add it to 4000g of water. Heat at 70℃ for 30min to obtain a heat-treated aqueous solution of organic polymer. Add 300g of boehmite (70% dry basis content, specific surface area 320m²) 2 A mixture of 160g of an aqueous solution of a heat-treated organic polymer (with a pore volume of 0.98mL / g) and 147g of corn starch was first mixed with 160.0g of 20wt% ammonia solution, and then granulated to obtain carrier precursor A. This precursor was then dried at 110℃ for 8 hours and calcined at 600℃ for 2 hours under a nitrogen atmosphere to obtain carrier A. 2Material B was prepared by mixing materials (0.98 mL / g, pore volume 0.98 mL / g). Support A was placed in a ball rolling mill, and during the rolling process, material B and 2000 g of a heated organic polymer aqueous solution were added to obtain support precursor B. Support precursor B was then heat-treated at 300℃ for 2 h to obtain support precursor C. 1167 g of basic nickel carbonate was dissolved in 1920 mL of a 20 wt% ammonia solution, then mixed with support precursor C, and dried at 120℃ for 8 h to obtain a catalyst precursor. 2453 g of nickel nitrate and 4620 g of zinc nitrate were dissolved in 1920 mL of water, then added to the catalyst precursor. After standing for 2 h, it was dried at 120℃ for 8 h and calcined at 550℃ for 3 h to obtain a spherical catalyst with a particle size of 0.5–0.8 mm, containing 30.0 wt% NiO and 30.0 wt% ZnO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0080] (2) Catalyst Evaluation

[0081] Cyclohexane-dissolved petroleum resin was used as raw material, with a petroleum resin mass fraction of 30%. The hydrogenation reaction was carried out in a fixed-bed tubular reactor. The reaction conditions were as follows: the reactor hydrogen pressure was increased to 15.0 MPa, the temperature was 400℃, the catalyst was reduced for 8 hours, and after the reduction was completed, the temperature was lowered to 260℃ to start the reaction again, with a volume hourly space velocity of 1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio (relative to the diluted feedstock) is 600:1. The properties of the petroleum resin are shown in Table 2, and the evaluation results are shown in Table 3.

[0082] Example 4

[0083] The process was essentially the same as in Example 3, except that corn starch was replaced with wheat flour, 1167g of basic nickel carbonate was replaced with 1492g of nickel acetate, and the calcination temperature was adjusted to 500℃ for 4 hours. Spherical catalysts with a particle size of 0.5–0.8 mm were obtained, containing 30.0 wt% NiO and 30.0 wt% ZnO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0084] The catalyst was evaluated in the same way as in Example 3. The properties of the feedstock oil used are shown in Table 2, and the evaluation results are shown in Table 3.

[0085] Comparative Example 1

[0086] (1) Catalyst preparation

[0087] 300g of pseudoboehmite (70% dry basis content, specific surface area 320m²) was used. 2The mixture of corn starch (70% dry basis content, 0.98 mL / g pore volume) and water was homogeneous and then pelletized to obtain carrier precursor A. This precursor was then dried at 110℃ for 8 hours and calcined at 600℃ for 2 hours under a nitrogen atmosphere to obtain carrier A. 147 g of corn starch was first mixed with 160.0 g of 20 wt% ammonia solution, and then mixed with 2100 g of pseudoboehmite (70% dry basis content, specific surface area 320 m² / g). 2 Material B was prepared by mixing materials A (with a pore volume of 0.98 mL / g) with a pore volume of 0.98 mL / g. Support A was placed in a ball rolling mill, and material B and 2000 g of water were added during the rolling process. After treatment, support precursor B was obtained. Support precursor B was heat-treated at 300℃ for 2 h to obtain support precursor C. 1167 g of basic nickel carbonate was dissolved in 1920 mL of 20 wt% ammonia solution, then mixed with support precursor C, and dried at 120℃ for 8 h to obtain catalyst precursor. 2453 g of nickel nitrate and 4620 g of zinc nitrate were dissolved in 1920 mL of water, then added to the catalyst precursor. After standing for 2 h, it was dried at 120℃ for 8 h and calcined at 550℃ for 3 h to obtain a spherical catalyst with a particle size of 0.5–0.8 mm, containing 30.0 wt% NiO and 30.0 wt% ZnO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0088] (2) Catalyst Evaluation

[0089] Cyclohexane-dissolved petroleum resin was used as raw material, with a petroleum resin mass fraction of 30%. The hydrogenation reaction was carried out in a fixed-bed tubular reactor. The reaction conditions were as follows: the reactor hydrogen pressure was increased to 15.0 MPa, the temperature was 400℃, the catalyst was reduced for 8 hours, and after the reduction was completed, the temperature was lowered to 260℃ to start the reaction again, with a volume hourly space velocity of 1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio (relative to the diluted feedstock) is 600:1. The properties of the petroleum resin are shown in Table 2, and the evaluation results are shown in Table 3.

[0090] Comparative Example 2

[0091] (1) Catalyst preparation

[0092] Weigh 240g of corn starch and add it to 4000g of water. Heat at 70℃ for 30min to obtain a heat-treated aqueous solution of organic polymer. Add 300g of boehmite (70% dry basis content, specific surface area 320m²) 2A mixture of 160g of an aqueous solution of a heat-treated organic polymer (70% dry basis, 0.98mL / g pore volume) and 160g of the polymer was homogeneous. After pelletizing, carrier precursor A was obtained, which was then dried at 110℃ for 8 hours and calcined at 600℃ for 2 hours under nitrogen atmosphere to obtain carrier A. This precursor was then mixed with [other materials] to obtain material B. Carrier A was placed in a pelletizing machine, and during the rolling process, 2100g of pseudoboehmite (70% dry basis, specific surface area 320m²) was added. 2 A solution of 2000g of an organic polymer (with a pore volume of 0.98mL / g) and heat-treated aqueous solution was used to obtain support precursor B. Support precursor B was then heat-treated at 300℃ for 2h to obtain support precursor C. 1167g of basic nickel carbonate was dissolved in 1920mL of a 20wt% ammonia solution, then mixed with support precursor C and dried at 120℃ for 8h to obtain catalyst precursor. 2453g of nickel nitrate and 4620g of zinc nitrate were dissolved in 1920mL of water, then added to the catalyst precursor. After standing for 2h, the mixture was dried at 120℃ for 8h and calcined at 550℃ for 3h to obtain a spherical catalyst with a particle size of 0.5–0.8mm, containing 30.0wt% NiO and 30.0wt% ZnO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0093] (2) Catalyst Evaluation

[0094] Cyclohexane-dissolved petroleum resin was used as raw material, with a petroleum resin mass fraction of 30%. The hydrogenation reaction was carried out in a fixed-bed tubular reactor. The reaction conditions were as follows: the reactor hydrogen pressure was increased to 15.0 MPa, the temperature was 400℃, the catalyst was reduced for 8 hours, and after the reduction was completed, the temperature was lowered to 260℃ to start the reaction again, with a volume hourly space velocity of 1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio (relative to the diluted feedstock) is 600:1. The properties of the petroleum resin are shown in Table 2, and the evaluation results are shown in Table 3.

[0095] Comparative Example 3

[0096] (1) Catalyst preparation

[0097] Weigh 240g of corn starch and add it to 4000g of water. Heat at 70℃ for 30min to obtain a heat-treated aqueous solution of organic polymer. Add 300g of boehmite (70% dry basis content, specific surface area 320m²) 2A mixture of 160g of an aqueous solution of a heat-treated organic polymer (with a pore volume of 0.98mL / g) and 147g of corn starch was first mixed with 160.0g of 20wt% ammonia solution, and then granulated to obtain carrier precursor A. This precursor was then dried at 110℃ for 8 hours and calcined at 600℃ for 2 hours under a nitrogen atmosphere to obtain carrier A. 2 Material B was prepared by mixing materials (NiO / g, pore volume 0.98 mL / g). Support A was placed in a ball rolling mill, and during the rolling process, material B and 2000 g of a heated organic polymer aqueous solution were added to obtain support precursor B. Support precursor B was then heat-treated at 300℃ for 2 h to obtain support precursor C. 4906 g of nickel nitrate and 4620 g of zinc nitrate were dissolved in 1920 mL of water and added to support precursor C. After standing for 2 h, the solution was dried at 120℃ for 8 h and calcined at 550℃ for 3 h to obtain a spherical catalyst with a particle size of 0.5–0.8 mm, containing 30.0 wt% NiO and 30.0 wt% ZnO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0098] (2) Catalyst Evaluation

[0099] Cyclohexane-dissolved petroleum resin was used as raw material, with a petroleum resin mass fraction of 30%. The hydrogenation reaction was carried out in a fixed-bed tubular reactor. The reaction conditions were as follows: the reactor hydrogen pressure was increased to 15.0 MPa, the temperature was 400℃, the catalyst was reduced for 8 hours, and after the reduction was completed, the temperature was lowered to 260℃ to start the reaction again, with a volume hourly space velocity of 1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio (relative to the diluted feedstock) is 600:1. The properties of the petroleum resin are shown in Table 2, and the evaluation results are shown in Table 3.

[0100] Table 1 Physicochemical properties of catalysts

[0101]

[0102] Table 2 Properties of Petroleum Resin Raw Materials

[0103] Resin softening point / °C 120 Colour (Saybolt) 8# S / μg·g -1 ]]> 142

[0104] Table 3 Catalyst Evaluation Results

[0105] Example Resin softening point / °C Colour (Saybolt) S / μg·g -1 ]]> Example 1 119 >+30 0.25 Example 2 118 >+30 0.30 Example 3 118 29 0.32 Example 4 117 29 0.30 Comparative Example 1 114 25 0.39 Comparative Example 2 106 26 0.36 Comparative Example 3 110 27 0.35

Claims

1. A method for preparing a petroleum resin hydrogenation catalyst, comprising the following steps: (1) Under mixed conditions, the pseudoboehmite and the aqueous solution of the heat-treated organic polymer were mixed evenly and then pelletized to obtain the carrier precursor A; (2) The carrier precursor A is obtained by drying and calcining the carrier; (3) Under mixing conditions, organic polymer, weakly basic compound and pseudoboehmite are mixed evenly to obtain material B; (4) Place carrier A into a ball rolling machine, and add material B obtained in step (3) and an aqueous solution of organic polymer after heat treatment during the rolling process. After treatment, carrier precursor B is obtained. The carrier precursor B obtained in step (4) was subjected to heat treatment under dry conditions to obtain carrier precursor C. (5) The support precursor C, nickel salt precursor and ammonia obtained in step (5) are mixed and dried after uniform mixing to obtain the catalyst precursor; (6) Introduce an active metal onto the catalyst precursor obtained in step (6), and then dry and calcine it to obtain a petroleum resin hydrogenation catalyst; in, The organic polymers in steps (1) and (3) are selected from one or more of starch, cellulose ether, and flour.

2. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The concentration of the aqueous solution of the heat-treated organic polymer in steps (1) and (4) is 0.5wt% to 5wt%, preferably 1wt% to 3wt%. The aqueous solution of the heat-treated organic polymer is prepared by adding the organic polymer to water and mixing it at 60 to 100°C for 10 to 40 minutes until the organic polymer is completely dissolved.

3. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The ratio of the amount of the heated organic polymer aqueous solution added in step (1) to the mass ratio of the pseudoboehmite is 0.5 to 1.

5.

4. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The starch is selected from at least one of mung bean starch, tapioca starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, and corn starch, preferably corn starch and / or potato starch; the cellulose ether is at least one of methylcellulose, hydroxyethyl methylcellulose, carboxymethylcellulose, ethylcellulose, benzylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, cyanoethylcellulose, benzyl cyanoethylcellulose, carboxymethyl hydroxyethylcellulose, and phenylcellulose, preferably methylcellulose.

5. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The drying temperature in step (2) is 80-140℃ and the drying time is 3-12h.

6. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The calcination in step (2) is carried out under an inert atmosphere. The calcination temperature in step (2) is 500-800℃ and the calcination time is 1-5h.

7. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The weakly alkaline compound in step (3) is selected from one or more of ammonia, ammonium carbonate, and ammonium bicarbonate, preferably ammonia.

8. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The mass ratio of the organic polymer and the weakly basic compound in step (3) is 1:0.05 to 1:0.

5.

9. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The organic polymer and weakly basic compound mentioned in step (3) are added in an amount of 5 wt% to 15 wt% of the dry basis of boehmite.

10. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The mass ratio of the aqueous solution of the heated organic polymer in step (4) to the mass of boehmite in step (3) is 0.5 to 1.

5.

11. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The heat treatment temperature in step (5) is 200-300℃, and the treatment time is 3-12h.

12. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The nickel salt precursor in step (6) is at least one of basic nickel carbonate, nickel nitrate, nickel acetate, and nickel sulfate.

13. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The active metals in step (7) are nickel and zinc.

14. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The active metal in step (7) is introduced by mixing the catalyst precursor with the active metal precursor and introducing it by impregnation. The active metal precursor includes nickel salt precursor and zinc salt precursor. The nickel salt precursor is one or more of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride; the zinc salt precursor is one or more of zinc nitrate, zinc sulfate, zinc acetate and zinc chloride.

15. The method for preparing the petroleum resin hydrogenation catalyst according to claim 1, wherein, The drying temperature in step (7) is 80-140℃ and the time is 3-12h; the roasting temperature in step (7) is 400-600℃ and the roasting time is 1-5h.

16. A petroleum resin hydrogenation catalyst obtained by the preparation method according to any one of claims 1-15.

17. The petroleum resin hydrogenation catalyst according to claim 16, wherein, The petroleum resin hydrogenation catalyst comprises an active metal component and a support. The active metal component is nickel oxide and zinc oxide, and the support is aluminum oxide. Based on the weight of the catalyst and calculated as oxides, the content of nickel oxide is 20wt% to 40wt%, and the content of zinc oxide is 10wt% to 30wt%.

18. The petroleum resin hydrogenation catalyst according to claim 16, wherein, The properties of petroleum resin hydrogenation catalysts are as follows: specific surface area is 120–220 m². 2 / g, with a pore volume of 0.50~0.70mL / g.

19. The application of the petroleum resin hydrogenation catalyst according to any one of claims 16-18 in the petroleum resin hydrogenation process.

20. The application according to claim 19, wherein, The petroleum resin is a C5 and / or C9 resin.

21. The application according to claim 19, wherein, The operating conditions for the hydrotreating process are: reaction pressure 8–20 MPa, reaction temperature 240–300 °C, and liquid hourly space velocity (LHSV) 0.3–2.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300–1000.

22. The application according to claim 19, wherein, Before use, the petroleum resin hydrogenation catalyst is subjected to reduction treatment at a pressure of 8–20 MPa, a temperature of 400–600 °C, and a time of 8–15 h.

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