Hydrogenation method of petroleum resin

Abstract

The present invention relates to the field of petroleum resin hydrogenation, and discloses a petroleum resin hydrogenation method, which comprises: carrying out a hydrogenation reaction on a petroleum resin solution in the presence of a hydrogenation catalyst, the preparation method of the hydrogenation catalyst comprises the following steps: (1) preparing a mixed solution containing an active metal source and a structure adjusting auxiliary agent, wherein the pH value of the mixed solution is 4-10; (2) dipping, drying and roasting the calcined alumina carrier in a mixed solution; wherein the structure adjusting auxiliary agent is a polycarboxyl-containing organic matter and / or amine; the active metal source includes a Ni source and a Group VIB metal source. When the catalyst is used for hydrofining petroleum resin, hydrogenated modified petroleum resin can be obtained, the quality of the petroleum resin is greatly improved, and meanwhile, the sulfur content in the petroleum resin is reduced.

Description

Technical Field

[0001] The present invention relates to the field of petroleum resin hydrogenation, and in particular to a petroleum resin hydrogenation method. Background Art

[0002] Petroleum resins are also commonly known as hydrocarbon resins. They are produced by processing the C5 and C9 fractions produced as byproducts of petroleum cracking to produce ethylene. After a series of processes such as raw material pretreatment, polymerization, catalyst removal, solvent removal, and curing molding, petroleum resins can be obtained in solid or viscous liquid form. Petroleum resins are oligomeric mixtures of thermoplastic resins. Their molecular weight is generally around 300-3000, and their softening point is 50-150°C. They have the characteristics of low acid value, low melting point, good miscibility, good adhesion, and resistance to water, acid, and alkali. According to the different raw materials, petroleum resins can be roughly divided into five types: (1) aliphatic petroleum resins based on C5 or C9 fractions; (2) aromatic petroleum resins based on C9 fractions; (3) copolymerized petroleum resins based on C5 and C9 fractions; (4) DCPD (dicyclopentadiene) alicyclic petroleum resins; and (5) petroleum resins that have been modified by hydrogenation.

[0003] Petroleum resins contain many unsaturated bonds in their molecular chains, making them easily oxidized, darker in color, and less stable. Furthermore, halide catalysts are often used in their synthesis, resulting in the product containing heteroatoms such as halogens and metals. Hydrogenated petroleum resins are produced by hydrogenating petroleum resins to convert unsaturated hydrocarbons into saturated hydrocarbons, improving their performance.

[0004] C5 petroleum resin is a polymer synthesized from olefins in the C5 fraction, a by-product of ethylene cracking. The C5 fraction accounts for approximately 14-17% of ethylene production. Its main components include n-pentane, isopentane, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, cyclopentadiene, isoprene, and others. C5 petroleum resin generally has a number-average molecular weight of no more than 2000. It is insoluble in water but readily soluble in organic solvents such as benzene, toluene, hexane, and gasoline. It exhibits excellent water resistance, acid and alkali resistance, and adhesion properties, and is commonly used as a tackifier. C5 petroleum resins are categorized by polymer raw material into decyclized C5 petroleum resin, isopentane petroleum resin, dicyclopentadiene petroleum resin, copolymerized petroleum resin, and mixed C5 petroleum resins. Petroleum resins are widely used in adhesives, coatings, inks, road marking paints, rubber, and papermaking.

[0005] Petroleum resin hydrogenation catalysts primarily include precious metal catalysts, such as Pd-based catalysts; non-precious metal Ni-based catalysts; and NiWS / NiMoS-based catalysts. Hydrogenation methods include single-stage and two-stage hydrogenation. In the two-stage method, the first stage typically pre-treats the petroleum resin, such as hydrodesulfurization, followed by deep hydrorefining in the second stage.

[0006] CN103386308A prepares a nickel-based catalyst supported on activated carbon with a nickel content of 3-8 wt %. Zn or Co is used as an additive with a content of 0.1-0.5 wt %. The hydrogenation reaction is carried out at 210°C and 9 MPa for 5 h. Only some examples have a conversion rate of more than 90%.

[0007] CN102935370A loads nickel on an alumina and titania composite carrier and hydrogenates the product at 160-220° C. and 4-7 MPa. The obtained hydrogenated petroleum resin has a bromine value lower than 1 gBr / 100 g, but a Gardner color higher than 1.

[0008] CN103386302A uses a Pd / Al2O3 catalyst with a Pd loading of 0.5-5wt%, a K2O content of 0.1-5%, a TiO2 content of 1-10%, and a Pd loading depth of 1-50 microns. The precious metal Pd loading is expensive, and the color of the C9 petroleum resin can only be reduced from 10# to 4#.

[0009] Therefore, in order to solve the problems existing in the prior art, a hydrogenation method with both high hydrogenation catalytic reaction activity and high stability is of great significance. Summary of the Invention

[0010] The present invention aims to overcome the problems in the prior art of hydrogenating petroleum resin using reduced Ni and Pt catalysts, which have a significant poisoning effect on the active centers of the catalyst, poor catalyst hydrogenation stability, and a high sulfur content in the hydrogenated product. A petroleum resin hydrogenation method is provided. The method comprises adding a structure regulating auxiliary agent during the preparation of the hydrogenation catalyst and limiting the pH value of the mixed solution to regulate the cluster morphology of the active metal Mo and / or W heteropolyacid therein. The active metal of the prepared hydrogenation catalyst is mainly loaded on the surface of an alumina carrier, and the catalyst has high hydrogenation activity and good stability.

[0011] In order to achieve the above object, the present invention provides a method for hydrogenating a petroleum resin, wherein the method comprises: subjecting a petroleum resin solution to a hydrogenation reaction in the presence of a hydrogenation catalyst;

[0012] The preparation method of the hydrogenation catalyst comprises:

[0013] (1) preparing a mixed solution containing an active metal source and a structure regulating agent, wherein the pH value of the mixed solution is 4-10;

[0014] (2) impregnating the calcined alumina support in the mixed solution, drying, and calcining;

[0015] Wherein, the structure regulating auxiliary agent is a polycarboxyl-containing organic matter and / or an amine substance; and the active metal source comprises a Ni source and a VIB group metal source.

[0016] Preferably, the pH value of the mixed solution is 4-6.

[0017] Preferably, the molar ratio of the structure regulating agent to the active metal is 0.25-2:1, preferably 0.4-1.2:1.

[0018] Through the above technical solution, the following beneficial effects are achieved:

[0019] The petroleum resin hydrogenation method provided by the present invention adjusts the cluster morphology of Mo or W heteropolyacid in the mixed solution by adding a structure regulating auxiliary agent and limiting the pH value of the mixed solution to prepare a hydrogenation catalyst. The active metal is mainly loaded on the outer surface of the alumina carrier, and the catalyst has high hydrogenation activity and good stability. The petroleum resin is hydrogenated and refined using the above catalyst to obtain hydrogenated modified petroleum resin, which greatly improves the quality of the petroleum resin and reduces the sulfur content in the petroleum resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the radial probe EPMA diagram of the catalyst of Preparation Example 1. DETAILED DESCRIPTION

[0021] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0022] One aspect of the present invention provides a petroleum resin hydrogenation method, wherein the method comprises: subjecting a petroleum resin solution to a hydrogenation reaction in the presence of a hydrogenation catalyst;

[0023] The preparation method of the hydrogenation catalyst comprises:

[0024] (1) preparing a mixed solution containing an active metal source and a structure regulating agent, wherein the pH value of the mixed solution is 4-10;

[0025] (2) impregnating the calcined alumina support in the mixed solution, drying, and calcining;

[0026] Wherein, the structure regulating auxiliary agent is a polycarboxyl-containing organic matter and / or an amine substance; and the active metal source comprises a Ni source and a VIB group metal source.

[0027] In the present invention, the petroleum resin hydrogenation method prepares a hydrogenation catalyst by adding a structure regulating auxiliary agent and limiting the pH value of the mixed solution to adjust the cluster morphology of the active metal Mo or W heteropoly acid therein. The active metal is mainly loaded on the outer surface of the alumina carrier, and the catalyst has high hydrogenation activity and good stability. The above catalyst is used to hydrogenate and refine the petroleum resin to obtain hydrogenated modified petroleum resin, which greatly improves the quality of the petroleum resin and reduces the sulfur content in the petroleum resin.

[0028] According to the present invention, preferably, the pH value of the mixed solution is 4-10, for example, 4, 5, 6, 7, 8, 9, 10, or any range therebetween, preferably 4-6. In the present invention, limiting the pH value of the mixed solution to the above range helps to adjust the aggregation morphology of the active metal, so that the active metal is mainly loaded on the outer surface of the support, which can improve the hydrogenation activity and stability of the catalyst.

[0029] In the present invention, the pH value of the mixed solution is adjusted by an acid and / or base. The acid and / or base are conventional acidic or alkaline substances in the art. Preferably, the acid is dilute nitric acid and the base is aqueous ammonia. The amount of the acid or base added is not particularly limited, and the pH value of the mixed solution can be adjusted to meet the above-mentioned limit. The base can be added when the acid is added in excess, or the acid can be added when the base is added in excess.

[0030] In the present invention, the mass concentration of the structure regulating agent in the mixed solution is not particularly limited.

[0031] According to the present invention, preferably, the molar ratio of the structure regulating agent to the active metal is 0.25-2:1, for example, 0.25:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, or any range therebetween, preferably 0.4-1.2: 1. In the present invention, the addition of the structure regulating agent helps to form clusters of the active metal, which are loaded on the surface of the alumina support during the subsequent loading process, thereby reducing the entry of the active metal into the internal pores of the alumina support, improving the utilization rate of the active metal, and improving the catalytic activity of the catalyst obtained.

[0032] According to the present invention, preferably, the structure-regulating agent is a polycarboxyl-containing organic compound and / or an amine-containing substance. The source of the structure-regulating agent is not particularly limited and can be purchased commercially or prepared by existing methods.

[0033] According to the present invention, preferably, the carboxyl-containing organic compound is selected from at least one of ethylenediaminetetraacetic acid, citric acid and oxalic acid.

[0034] According to the present invention, preferably, the amine substance is selected from at least one of ethylenediamine, triethylamine, tetrabutylammonium bromide and ammonia water. In the present invention, when the amine is ammonia water, the amount of the amine substance is the amount of NH3 in the ammonia water.

[0035] According to the present invention, preferably, the structure-regulating auxiliary agent is a polycarboxyl-containing organic compound or an amine substance, preferably ethylenediaminetetraacetic acid or oxalic acid.

[0036] According to the present invention, preferably, the amount of the alumina carrier and the mixed solution added is such that in the prepared catalyst, the mass percentage of nickel, calculated as nickel oxide, based on the total mass of the catalyst is 1-10wt%, for example, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, or any range therebetween, preferably 2-8wt%.

[0037] According to the present invention, preferably, the amount of the catalyst support and the mixed solution added is such that the mass percentage of the VIB Group metal in the prepared catalyst, calculated as oxide, based on the total mass of the catalyst is 10-30wt%, preferably 10-20wt%. For example, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt%, or any range therebetween, preferably 10-20wt%. In the present invention, the active components are loaded on the surface of a support having a rich pore structure, and the active components are loaded on the support surface in the form of clusters. The pore structure of the catalyst support facilitates the diffusion of reactant molecules on the catalyst surface, and in combination with the active components, facilitates the adsorption and reaction of petroleum resin macromolecules on the reactive centers. Compared with catalysts prepared using precious metal Pd, the sulfur content of the raw materials cannot be too high during the hydrogenation reaction of petroleum resin. The loaded active components have better resistance to sulfur shock and good adaptability to the sulfur content of the raw materials. They have high hydrogenation catalytic activity under conditions of sulfur content of 0-10%.

[0038] According to the present invention, preferably, the VIB Group metal source is a Mo source and / or a W source.

[0039] In the present invention, the type of the nickel source is not particularly limited and can be any conventional nickel source in the art. Preferably, the nickel source is selected from at least one of nickel sulfate, nickel nitrate, basic nickel carbonate and nickel chloride.

[0040] In the present invention, the type of the Mo source is not particularly limited and can be any conventional Mo source in the art. Preferably, the Mo source is molybdenum trioxide and / or ammonium molybdate. The type of the W source is not particularly limited and can be any conventional W source in the art. Preferably, the W source is tungsten trioxide and / or ammonium metatungstate.

[0041] According to the present invention, preferably, when the active metal source is a water-insoluble compound, citric acid is added to dissolve the active metal source. The amount of citric acid added is not particularly limited, so that the active metal source is fully dissolved, and those skilled in the art can adaptably adjust the amount of citric acid added. In the present invention, citric acid can also play a complexing role and a role in regulating the pH value of the mixed solution, regulating the cluster morphology of Mo and / or W heteropolyacids, so that the active metal is mainly loaded on the outer surface of the catalyst during the impregnation process.

[0042] According to the present invention, the calcined alumina support is preferably selected from at least one of γ-Al2O3, α-Al2O3, and β-Al2O3, preferably γ-Al2O3. The source of the alumina support is not particularly limited and can be commercially available or prepared by existing methods, as long as it can achieve the objectives of the present invention. According to a preferred embodiment of the present invention, the alumina support is prepared by extrusion molding, and those skilled in the art can adapt the extrusion molding conditions.

[0043] According to the present invention, preferably, the most probable pore size of the calcined alumina support is 7-18 nm, for example, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, or any range therebetween, preferably 7-15 nm, more preferably 7-10 nm.

[0044] In the present invention, the most probable pore size has the conventional meaning in the art, and refers to the pore size corresponding to the most concentrated pore distribution. The most probable pore size is obtained by BET method testing, and the pore size corresponding to the peak value is obtained by plotting the pore distribution measured by BET.

[0045] According to the present invention, preferably, the specific surface area of ​​the calcined alumina carrier is 120-250m 2 / g, for example 120m 2 / g、135m 2 / g, 150m 2 / g、165m 2 / g, 180m 2 / g, 200m 2 / g, 210m 2 / g, 235m 2 / g, 250m 2 / g, or any range between the two, preferably 150-210m 2In the present invention, the calcined alumina carrier meets the above-defined minimum pore size and specific surface area, and the active metals are loaded in clusters on the surface of the alumina carrier, which reduces the entry of active metals into the carrier pores and improves the utilization rate of the active metals.

[0046] In the present invention, the pore volume of the calcined alumina carrier is 0.3-0.9 cm 3 / g, preferably 0.45-0.8cm 3 / g. The specific surface area and pore volume of the calcined alumina support were measured using the BET low-temperature nitrogen adsorption method using a Micromeritics ASAP2400 static nitrogen adsorption instrument. Test conditions: The sample was vacuum degassed at 1.33 Pa and 300°C for 4 hours, then exposed to liquid nitrogen at 77 K for isothermal adsorption and desorption. The adsorption and desorption isotherms were measured, and the specific surface area and pore volume of the alumina support were calculated using the BET formula.

[0047] According to the present invention, preferably, the calcination conditions include: a calcination temperature of 350-780° C., preferably 380-550° C.; and a calcination time of 2-8 h, preferably 3-6 h.

[0048] According to the present invention, preferably, the heating rate of the calcination is 2-8°C / min, preferably 3-5°C / min. In the present invention, the calcination is carried out under the above conditions, and the alumina carrier is calcined at a high temperature to improve the pore structure of the carrier.

[0049] In the present invention, the equipment for calcining is not particularly limited, and preferably, the calcining is carried out in a tube furnace and in an air flow.

[0050] In the present invention, the impregnation conditions are not particularly limited, and those skilled in the art can select conventional impregnation conditions, preferably an equal volume impregnation method.

[0051] According to the present invention, the drying method and drying conditions are not particularly limited, and those skilled in the art can select conventional drying methods and drying conditions. Preferably, the drying conditions include: a drying temperature of 100-200° C. and a drying time of 1-5 hours.

[0052] According to the present invention, preferably, the calcination conditions include: a calcination temperature of 300-480°C, preferably 320-420°C, in an air flow; and a calcination time of 2-8 hours, preferably 3-6 hours. In the present invention, calcination in an air flow can avoid insufficient oxygen during calcination, which can cause carbonization of organic matter in the catalyst and reduce catalytic activity.

[0053] According to the present invention, preferably, the heating rate of the calcination is 1-8°C / min, preferably 2-6°C / min.

[0054] In the present invention, preferably, the hydrogenation catalyst comprises alumina and an active metal supported on the outer surface of the alumina. Figure 1 As shown, scanning electron microscope EPMA probe analysis observed that the active metal in the hydrogenation catalyst was supported on the outer surface of alumina.

[0055] According to the present invention, preferably, the mass concentration of the petroleum resin solution is 5-30wt%, such as 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, or any range therebetween, preferably 15-25wt%.

[0056] In the present invention, the petroleum resin has a conventional definition in the art, and is preferably selected from at least one of C5 petroleum resin, C9 petroleum resin and DCPD petroleum resin, and more preferably C5 petroleum resin.

[0057] According to the present invention, the solvent of the petroleum resin solution is preferably selected from at least one of toluene, mesitylene, xylene, n-octane, petroleum ether, cyclohexane, methylcyclohexane, D40 solvent oil, and n-heptane, and is preferably selected from at least one of cyclohexane, methylcyclohexane, n-heptane, D40 solvent oil, and toluene. In the present invention, the D40 solvent oil has the conventional meaning in the art, and refers to a distillate obtained by fractionation after 130kPa high-pressure hydrorefining using distillate oil as a raw material. Using the above solvent to dissolve the petroleum resin can obtain a solution with good fluidity, low viscosity, and uniform stability.

[0058] In the present invention, preferably, the petroleum resin is dissolved in a solvent and ultrasonically assisted in the dissolution. The ultrasonic conditions are not particularly limited and are conventional ultrasonic conditions in the art. The ultrasonic-assisted method can promote the formation of a uniform and stable solution of the macromolecular petroleum resin in the solvent.

[0059] According to the present invention, preferably, the method further comprises the step of subjecting the hydrogenation catalyst to a sulfurization treatment before the hydrogenation reaction.

[0060] According to the present invention, preferably, the sulfurization treatment process comprises: in the presence of a mixed gas containing a sulfur source, the sulfurization temperature is 250-450° C., and the sulfurization time is 3-20 hours.

[0061] In the present invention, the sulfur source is hydrogen sulfide gas, and the mixed gas comprises hydrogen sulfide gas and hydrogen, with the volume percentage of hydrogen sulfide being 2-4%. The mixed gas containing the sulfur source is introduced under the aforementioned sulfurization conditions to perform ex-situ sulfurization on the hydrogenation catalyst to obtain a sulfurized NiW(Mo)S / Al2O3 catalyst, which can improve the catalyst's hydrogenation catalytic activity and stability.

[0062] In the present invention, the sulfurized catalyst exhibits excellent hydrogenation performance, particularly avoiding the problem of reduced metal sulfur poisoning. Hydrorefining petroleum resin using the sulfurized catalyst can yield hydrogenated, modified petroleum resin, significantly improving its quality. Furthermore, it can also serve as a pretreatment technology for pre-desulfurization of petroleum resin, significantly reducing its sulfur content and providing cleaner material for subsequent deep hydrogenation with reduced metals.

[0063] According to the present invention, preferably, the conditions of the hydrogenation reaction include: being carried out under hydrogen conditions, the reaction equilibrium system pressure is 1-18 MPa, the reaction temperature is 200-340°C, the reaction time is 1-10 hours, and the mass ratio of petroleum resin to sulfurized catalyst is 2-6.

[0064] According to the present invention, preferably, the conditions for the hydrogenation reaction include: being carried out under hydrogen conditions, the reaction equilibrium system pressure is 6-15 MPa, the reaction temperature is 220-300°C, the reaction time is 2-5 hours, and the mass ratio of petroleum resin to sulfurized catalyst is 3-5.

[0065] In the present invention, the equipment for the hydrogenation reaction is not particularly limited, and those skilled in the art can adaptably select the equipment for the hydrogenation reaction. Preferably, the hydrogenation reaction is carried out in a high-pressure reactor.

[0066] In the present invention, preferably, the hydrogenation reaction is carried out under stirring conditions, and the stirring rate is not particularly limited, as long as sufficient mass transfer effect is achieved. Preferably, the stirring rate is 200-500 rpm.

[0067] In the present invention, the hydrogenation reaction is carried out under the above conditions using the aforementioned hydrogenation catalyst, and the overall impurity removal activity and hydrogenation saturation performance are good, the sulfur removal rate in the petroleum resin is high, and the sulfur content and ash content are low.

[0068] According to the present invention, the product of the hydrogenation reaction is preferably separated by vacuum distillation. The conditions for the vacuum distillation are not particularly limited. Preferably, the conditions for the vacuum distillation include: a pressure in the evaporation apparatus of <50 mBar and an oil bath heating temperature of 70-160°C. According to a preferred embodiment of the present invention, the vacuum distillation conditions meet the above-mentioned requirements by evacuating the air using a vacuum pump.

[0069] In the present invention, the product of the hydrogenation reaction is subjected to reduced pressure distillation to evaporate the solvent to obtain a hydrogenated petroleum resin product, which is colorless or nearly colorless.

[0070] In the present invention, the sulfur content of the petroleum resin is determined using energy dispersive X-ray fluorescence spectrometry. A certain mass of petroleum resin is dissolved in a certain mass of analytically pure hydrocarbon solvent. The sample is placed in a beam of radiation emitted from an X-ray source. The excitation energy can be obtained from a radioactive source or an X-ray tube. The intensity of the sulfur Kα characteristic spectral line with an energy of 2.3 keV is measured, and the accumulated intensity is compared with the intensity of a pre-prepared calibration sample to obtain the sulfur content expressed as a mass percentage, thereby determining the sulfur content of the petroleum resin.

[0071] In the present invention, the bromine value of the petroleum resin is determined using a coulometric method. A certain mass of petroleum resin is dissolved in a certain mass of an analytically pure saturated hydrocarbon solvent. The sample is then injected into an electrolyte containing a known amount of bromine. The double bonds in the sample react with the bromine, and the bromine consumed in the reaction is replenished by electrolysis. The amount of electricity consumed to replenish the bromine is measured, and the bromine value or bromine index of the sample can be calculated based on Faraday's law of electrolysis. Ash content is determined using the petroleum product ash content determination method. The sample is burned using ashless filter paper as a wick, and the carbonized residue is then calcined to constant weight. Gardner colorimetry is obtained using a colorimetric method.

[0072] In the present invention, the sulfur removal rate of the petroleum resin after hydrogenation reaction is greater than 85%, the bromine value is 0.8-5gBr / 100g, the ash content is less than 0.2wt%, and the Gardner chromaticity is less than 1#.

[0073] The present invention will be described in detail below through examples and comparative examples. In the following examples and comparative examples, unless otherwise specified, all reagents used in the present invention are commercially available;

[0074] The test methods for the pore structure of the catalyst support, the active metal content, and the physicochemical properties of the petroleum resin in the hydrogenation catalyst are described in the aforementioned specification and will not be repeated here.

[0075] Catalyst Preparation Example 1

[0076] (1) 50 g of γ-Al2O3 carrier dry strips were calcined in a tubular furnace at 500°C for 3 h under air flow at a heating rate of 5°C / min to obtain a calcined alumina carrier. The calcined alumina carrier had a maximum pore size of 10 nm and a specific surface area of ​​176 m 2 / g, the pore volume of the alumina support is 0.48cm 3 / g.

[0077] (2) Nickel nitrate and ammonium metatungstate were weighed and dissolved in water, respectively. 12 g of ethylenediaminetetraacetic acid (EDTA) was added, and the pH of the solution was adjusted with aqueous ammonia and dilute nitric acid to a pH of 5.6. The active metals were impregnated onto a calcined alumina support by an equal volume impregnation method to obtain a catalyst having a Ni content of 4 wt% (calculated as NiO) and a W content of 18 wt% (calculated as WO3). The catalyst was dried at 120°C and then calcined at 400°C for 3 h at a heating rate of 5°C / min to obtain Catalyst 1.

[0078] The shape of the catalyst in Preparation Example 1 is approximately butterfly-shaped. The width of the catalyst at its widest radial point measured with a vernier caliper is 1.5 mm. Figure 1 This is the radial probe EPMA diagram of the catalyst of Preparation Example 1. Figure 1 It can be seen that the red area indicates the concentrated distribution of active metal elements. Active metals tend to concentrate on the outer surface of the catalyst, which helps to improve the utilization efficiency of active metals.

[0079] Catalyst Preparation Example 2

[0080] (1) The same calcined alumina carrier as in Catalyst Preparation Example 1 was used.

[0081] (2) Basic nickel carbonate and molybdenum trioxide were weighed and dissolved in an aqueous solution containing 15 g of citric acid. The pH of the solution was adjusted with citric acid and aqueous ammonia to a pH of 5.0. The active metals were impregnated onto the support by an equal volume impregnation method to obtain a catalyst having a Ni content of 2.5 wt% (calculated as NiO) and a Mo content of 16.5 wt% (calculated as MoO3). The catalyst was dried at 120°C and calcined at 420°C for 3 h at a heating rate of 5°C / min to obtain Catalyst 2.

[0082] Catalyst Preparation Example 3

[0083] According to the method of Catalyst Preparation Example 1, the same calcined alumina carrier as that in Catalyst Preparation Example 1 was used, except that the structure regulating agent was replaced by 5 g of oxalic acid in step (2). Other conditions were the same as those in Catalyst Preparation Example 1. The mass percentage of Ni in the catalyst was 4 wt% (calculated as NiO), and the mass percentage of W was 18 wt% (calculated as WO3), to obtain Catalyst 3.

[0084] Catalyst Preparation Example 4

[0085] The method of catalyst preparation example 1 was followed, except that the alumina carrier was changed. The most probable pore size of the alumina carrier after calcination was 18 nm, and the specific surface area of ​​the alumina carrier was 185 m 2 / g, the pore volume of the alumina support is 0.54 cm 3 / g.

[0086] Other conditions were the same as those in Catalyst Preparation Example 1. The mass percentage of Ni in the catalyst was 4 wt% (calculated as NiO), and the mass percentage of W was 18 wt% (calculated as WO3), to obtain Catalyst 4.

[0087] Catalyst Preparation Example 5

[0088] The method of Catalyst Preparation Example 1 was followed, using the same calcined alumina support as in Catalyst Preparation Example 1. The difference was that the pH of the impregnation solution in step (2) was adjusted by using aqueous ammonia and dilute nitric acid to a mixed solution pH of 8.2. Other conditions were the same as those in Catalyst Preparation Example 1. The mass percentage of Ni in the catalyst was 4 wt% (calculated as NiO), and the mass percentage of W was 18 wt% (calculated as WO3), to obtain Catalyst 5.

[0089] Catalyst Comparative Example 1

[0090] The method of Catalyst Preparation Example 1 was followed, except that in step (2), the catalyst obtained by the impregnation method was dried at 120°C and then calcined at 320°C in a nitrogen stream. The resulting catalyst was designated "Comparative Agent 1." Based on the total mass of the catalyst, the mass percentage of Ni was 4 wt% (calculated as NiO), and the mass percentage of W was 18 wt% (calculated as WO3).

[0091] Catalyst Comparative Example 2

[0092] The method of Catalyst Preparation Example 1 was followed, except that no structure-regulating agent was added to the mixed solution in step (2). The pH of the mixed solution was adjusted to 5.4 using aqueous ammonia and dilute nitric acid. The impregnation, drying, and calcination conditions were the same as those in Catalyst Preparation Example 1. The resulting catalyst was designated "Comparative Agent 2." Based on the total mass of the catalyst, the mass percentage of Ni was 4 wt% (calculated as NiO), and the mass percentage of W was 18 wt% (calculated as WO3).

[0093] Catalyst Comparative Example 3

[0094] An alumina support was prepared according to the method of step (1) of Catalyst Preparation Example 1. (2) 0.5 g of palladium nitrate was weighed and dissolved in water, 0.55 g of ethylenediaminetetraacetic acid (EDTA) was added, and the pH of the solution was adjusted with ammonia water and dilute nitric acid to a pH of 5.6. The active metal was impregnated onto the calcined alumina support by an equal volume impregnation method, dried at 120° C., and then calcined at 400° C. for 3 h at a heating rate of 5° C. / min. The mass percentage of Pd in ​​the catalyst was 0.6 wt %, recorded as "Comparative Agent 3", and used for sulfur resistance testing.

[0095] Examples 1-5, Comparative Examples 1-2

[0096] The prepared catalyst was used to carry out a petroleum resin hydrogenation reaction. The raw material of the hydrogenated petroleum resin was C5 petroleum resin. The physicochemical properties of the petroleum resin are shown in Table 1.

[0097] Table 1

[0098]

[0099]

[0100] Hydrogenation reaction conditions: 30g of C5 petroleum resin, 120g of solvent, and 8g of pre-sulfurized catalyst were added to an autoclave. Sulfurization conditions were: a 2.5% H2S / H2 gas mixture at 300°C for 4 hours.

[0101] After sealing the autoclave, hydrogen was introduced after nitrogen replacement and stirring at 500 rpm to dissolve the petroleum resin. After stirring for a period of time, a temperature ramp was initiated, and the reaction was maintained at 260°C for 3 hours, with an equilibrium hydrogen pressure of 9.8 MPa. After the temperature dropped to room temperature, a nitrogen purge was performed. The autoclave was opened, the solution was filtered to separate the catalyst particles, and the solvent was evaporated under reduced pressure. The reaction results are shown in Table 2.

[0102] Table 2

[0103]

[0104] The results in Table 2 indicate that the catalysts prepared using the preparation methods of the embodiments of the present invention have active metal elements concentrated on the catalyst's outer surface, resulting in high active metal utilization. Under the same reaction conditions, the catalysts prepared using the embodiments of the present invention, when used in petroleum resin hydrogenation reactions, produce products with lower sulfur content, higher desulfurization rates, lower ash content, and lower Gardner chroma compared to the catalysts prepared in the comparative examples, demonstrating superior hydrogenation performance. However, when a structure modifier is not added during the active metal impregnation process or the pH of the mixed solution is too high, the active metals enter the pores of the alumina support, reducing active metal utilization. Consequently, when used in petroleum resin hydrogenation reactions, the product exhibits high sulfur content, low desulfurization rates, high bromine values, ash content, and chroma, resulting in poor hydrogenation performance.

[0105] Sulfur resistance test

[0106] A petroleum resin hydrogenation reaction was carried out in an autoclave by supplementing an additional sulfur source. The sulfur resistance of the sulfurized catalyst of catalyst 1 and the precious metal catalyst of comparative agent 3 were compared. CS2 was added to the petroleum resin raw material in the autoclave in an amount such that the amount of sulfur element was three times the amount of active metal substance in the corresponding catalyst. The physicochemical properties of the petroleum resin raw material are shown in Table 1. The conditions for hydrogenation of the petroleum resin were the same as those in Examples 1-5 and Comparative Examples 1-2. The properties of the obtained petroleum resin product are shown in Table 3.

[0107] Table 3

[0108]

[0109] The results in Table 3 show that the sulfurized catalyst prepared using the preparation method of the present invention has strong sulfur resistance. Comparative Agent 3, a noble metal Pd catalyst, rapidly deactivates and loses its hydrogenation performance due to the introduction of a large amount of sulfur into the system, which is three times the amount of active metal.

[0110] Example 6

[0111] The petroleum resin was hydrogenated using catalyst 1. The raw material of the hydrogenated petroleum resin was C5 petroleum resin. The physicochemical properties of the petroleum resin are shown in Table 1.

[0112] Hydrogenation reaction conditions: 30g of C5 petroleum resin and 120g of solvent were mixed and ultrasonicated for 30 minutes to obtain a homogeneous and stable solution. The petroleum resin solution was transferred to an autoclave and 8g of pre-sulfurized catalyst 1 was added.

[0113] The curing conditions were: a temperature of 300°C for 4 hours in a mixed gas stream containing 2.5% H₂S / H₂. The autoclave was sealed, replaced with nitrogen, and then introduced with hydrogen. The stirring rate was increased to 300 rpm, and a temperature ramp was initiated. The reaction was maintained at 280°C for 3 hours, with an equilibrium hydrogen pressure of 10.6 MPa. After the temperature dropped to room temperature, a nitrogen purge was performed. The autoclave was opened, the solution was filtered to separate the catalyst particles, and the solvent was evaporated under reduced pressure. The reaction results are shown in Table 4.

[0114] Example 7

[0115] The petroleum resin was hydrogenated using catalyst 1. The raw material of the hydrogenated petroleum resin was C5 petroleum resin. The physicochemical properties of the petroleum resin are shown in Table 1.

[0116] Hydrogenation reaction conditions: 30 g of C5 petroleum resin and 120 g of solvent were mixed, dissolved and dispersed with ultrasound assistance, and added to an autoclave. 8 g of pre-sulfurized Catalyst 1 was then added. The vulcanization conditions were: a vulcanization temperature of 300°C and a vulcanization time of 4 hours in a gaseous stream containing 2.5% H2S / H2. The autoclave was sealed, and hydrogen was introduced after nitrogen displacement. The stirring rate was increased to 300 rpm, and a temperature ramp was initiated. The reaction was maintained at 220°C for 3 hours, with an equilibrium hydrogen pressure of 9.1 MPa. After the temperature dropped to room temperature, a nitrogen purge was performed. The autoclave was opened, the solution was filtered to separate the catalyst particles, and the solvent was evaporated under reduced pressure. The reaction results are shown in Table 4.

[0117] Example 8

[0118] The petroleum resin was hydrogenated using catalyst 1. The raw material of the hydrogenated petroleum resin was C5 petroleum resin. The physicochemical properties of the petroleum resin are shown in Table 1.

[0119] Hydrogenation reaction conditions: 30 g of C5 petroleum resin and 120 g of solvent were mixed, dissolved and dispersed with the assistance of ultrasound, added to an autoclave, and then 8 g of pre-sulfurized catalyst 1 was added.

[0120] The curing conditions were: a temperature of 300°C for 4 hours in a mixed gas stream containing 2.5% H₂S / H₂. The autoclave was sealed, replaced with nitrogen, and then introduced with hydrogen. The stirring rate was increased to 300 rpm, and a temperature ramp was initiated. The reaction was maintained at 220°C for 3 hours, with the equilibrium hydrogen pressure at 12.4 MPa. After the temperature dropped to room temperature, a nitrogen purge was performed. The autoclave was opened, the solution was filtered to separate the catalyst particles, and the solvent was evaporated under reduced pressure. The reaction results are shown in Table 4.

[0121] Table 4

[0122]

[0123]

[0124] As can be seen from Table 4, when catalyst 1 is used for the hydrogenation reaction of petroleum resin under different conditions, Example 6 has a high hydrogenation reaction temperature, a low sulfur content in the hydrogenation reaction product, a high desulfurization rate, a lower bromine value, a lower ash content, a low Gardner chroma, and good desulfurization and hydrogenation effects.

[0125] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A method for hydrogenating a petroleum resin, characterized in that: The method comprises: subjecting a petroleum resin solution to a hydrogenation reaction in the presence of a hydrogenation catalyst; The preparation method of the hydrogenation catalyst comprises: (1) preparing a mixed solution containing an active metal source and a structure regulating agent, wherein the pH value of the mixed solution is 4-10; (2) impregnating the calcined alumina support in the mixed solution, drying, and calcining; Wherein, the structure regulating auxiliary agent is a polycarboxyl-containing organic matter and / or an amine substance; and the active metal source comprises a Ni source and a VIB group metal source.

2. The hydrogenation method according to claim 1, wherein The pH value of the mixed solution is 4-6; Preferably, the molar ratio of the structure regulating agent to the active metal is 0.25-2:1, preferably 0.4-1.2:1; Preferably, the carboxyl-containing organic compound is selected from at least one of ethylenediaminetetraacetic acid, citric acid and oxalic acid; Preferably, the amine substance is selected from at least one of ethylenediamine, triethylamine, tetrabutylammonium bromide and ammonia water.

3. The hydrogenation method according to claim 1 or 2, wherein The amount of the alumina carrier and the mixed solution added is such that the mass percentage of nickel in the prepared catalyst is 1-10 wt %, preferably 2-8 wt %, based on the total mass of the catalyst and calculated as nickel oxide; Preferably, the catalyst support and the mixed solution are added in such an amount that the mass percentage of the VIB group metal in the prepared catalyst, calculated as oxide, based on the total mass of the catalyst is 10-30 wt%, preferably 10-20 wt%; Preferably, the VIB Group metal source is a Mo source and / or a W source.

4. The hydrogenation method according to any one of claims 1 to 3, wherein The calcined alumina carrier is selected from at least one of γ-Al2O3, α-Al2O3 and β-Al2O3, preferably γ-Al2O3; Preferably, the most probable pore size of the calcined alumina support is 7-18 nm, preferably 7-15 nm; Preferably, the specific surface area of ​​the calcined alumina carrier is 120-250 m 2 / g, preferably 150-210m 2 / g.

5. The hydrogenation method according to any one of claims 1 to 4, wherein The calcination conditions include: calcination temperature of 350-780°C, preferably 380-550°C; calcination time of 2-8h, preferably 3-6h; Preferably, the heating rate of the calcination is 2-8°C / min, preferably 3-5°C / min.

6. The hydrogenation method according to any one of claims 1 to 5, wherein The calcination conditions include: in an air flow, a calcination temperature of 300-480°C, preferably 320-420°C; a calcination time of 2-8 hours, preferably 3-6 hours; Preferably, the heating rate of the calcination is 1-8°C / min, preferably 2-6°C / min.

7. The hydrogenation method according to any one of claims 1 to 6, wherein: The mass concentration of the petroleum resin solution is 5-30wt%, preferably 15-25wt%; Preferably, the solvent of the petroleum resin solution is selected from at least one of toluene, mesitylene, xylene, n-octane, petroleum ether, cyclohexane, methylcyclohexane, D40 solvent oil and n-heptane, preferably selected from at least one of cyclohexane, methylcyclohexane, n-heptane, D40 solvent oil and toluene.

8. The hydrogenation method according to any one of claims 1 to 7, wherein: It also includes the process of sulfurizing the hydrogenation catalyst before the hydrogenation reaction; Preferably, the sulfurization treatment process includes: in the presence of a mixed gas containing a sulfur source, the sulfurization temperature is 250-450° C., and the sulfurization time is 3-20 hours.

9. The hydrogenation method according to any one of claims 1 to 8, wherein The conditions of the hydrogenation reaction include: carrying out the reaction under hydrogen conditions, the reaction equilibrium system pressure is 1-18 MPa, the reaction temperature is 200-340° C., the reaction time is 1-10 hours, and the mass ratio of petroleum resin to sulfurized catalyst is 2-6.

10. The hydrogenation method according to claim 9, wherein The conditions for the hydrogenation reaction include: carrying out the reaction under hydrogen conditions, the reaction equilibrium system pressure is 6-15 MPa, the reaction temperature is 220-300° C., the reaction time is 2-5 hours, and the mass ratio of the petroleum resin to the vulcanized catalyst is 3-5; Preferably, the product of the hydrogenation reaction is separated by vacuum distillation, and the conditions of the vacuum distillation include: the pressure in the evaporation device is less than 50mBar, and the oil bath heating temperature is 70-160°C.

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