A catalytic hydrogenation method for C5 resin

Abstract

The present invention discloses a method for catalytic hydrogenation of C5 resin, which is characterized by the following steps: (1) putting a Ni-W-Pr / silica gel coprecipitation catalyst in the first half of a fixed bed and a Zr-Sr-Nd / aluminum hydroxide coprecipitation catalyst in the second half of the fixed bed, and introducing hydrogen for reduction; (2) catalytically hydrogenating the pretreated C5 resin in the fixed bed. Compared with the prior art, the method for catalytic hydrogenation of C5 resin of the present invention has high catalytic efficiency and simple process, and the catalytic hydrogenation method can obtain products with good colority and low bromine value.

Description

Technical Field

[0001] The present invention relates to the technical field of catalytic hydrogenation of petroleum resins, and specifically refers to a method for catalytic hydrogenation of C5 resins. Background Art

[0002] C5 (C5) is a by-product obtained during the cracking to produce ethylene. C5 is directly polymerized to produce C5 petroleum resin. C5 petroleum resin is widely used in industries such as coatings, rubber, inks, adhesives, etc. However, ordinary C5 petroleum resins have problems such as poor color difference, poor thermal stability and chemical stability during use. They will produce unpleasant odors when heated and their colors are likely to darken under long-term light exposure, which greatly limits their application scope. This is because the double bonds formed during the resin synthesis process are chemically unstable. Currently, in order to improve the quality of C5 petroleum resin, catalytic hydrogenation processes are commonly used at home and abroad to saturate the double bonds in C5 petroleum resin, and at the same time, the halides remaining during the polymerization process are also removed. After the resin is hydrogenated, it can become a white or transparent, highly stable and miscible C5 hydrogenated petroleum resin.

[0003] The hydrogenation process of C5 petroleum resin started in the 1970s abroad. By the 1980s, hydrogenated C5 petroleum resin could be produced on a large scale. One of the keys to the industrialization of C5 petroleum resin hydrogenation technology is the poison resistance of the catalyst. Generally, it is considered that the poisons of resin hydrogenation catalysts are impurities such as gels, S, and Cl. Gels are produced during the resin polymerization process, and their content mainly depends on the resin polymerization process. Gels are the precursors of carbon deposition on the surface of the hydrogenation catalyst, which can cause the catalyst to quickly deactivate. Currently, the main C5 petroleum resin hydrogenation catalysts are palladium and nickel-based hydrogenation catalysts. In US Patent US3040009, a nickel catalyst supported on pre-activated diatomaceous earth was used for the hydrogenation reaction of C5 petroleum resin. The thermally polymerized petroleum resin was dissolved in a saturated hydrocarbon solvent (such as heptane), and then hydrogenated at 210 - 230 °C and 3.0 - 9.1 MPa for 5 - 7 h. The yield of the obtained hydrogenated petroleum resin was 90 - 95% (based on the raw material polymerized resin), and the bromine value was 1 - 3 gBr 2 / 100 g. The disadvantage is that the catalyst life is short. The Ni35 - 50 wt% / Al 2 0 3 catalyst catalyzes the hydrogenation of C5 / C9 copolymer petroleum resin in a fixed bed to prepare a high-performance hydrogenated petroleum resin with a Gardner color less than 3 and a softening point above 85 °C, and the catalyst has a certain stability.

[0004] In summary, the current C5 resin hydrogenation catalysts have problems such as uneven dispersion of the catalyst on the support, poor catalytic effect, and short catalyst life. Therefore, it is necessary to develop a method for catalytic hydrogenation of C5 resin with high catalytic efficiency and simple process. Summary of the Invention

[0005] Aiming at the current situation of the prior art, the technical problem to be solved by the present invention is to provide a catalytic hydrogenation method for C5 resin with high catalytic efficiency and simple process, and the catalytic hydrogenation method can obtain products with good colority and low bromine value.

[0006] The technical solution adopted by the present invention to solve the technical problem is as follows: A catalytic hydrogenation method for C5 resin, which is characterized by including the following steps:

[0007] (1) Put the Ni-W-Pr / silica gel coprecipitation catalyst in the first half of the fixed bed, put the Zr-Sr-Nd / aluminum hydroxide coprecipitation catalyst in the second half of the fixed bed, and introduce hydrogen for reduction;

[0008] (2) Catalytically hydrogenate the pretreated C5 resin in the fixed bed.

[0009] Preferably, the specific preparation method of the Ni-W-Pr / silica gel coprecipitation catalyst is as follows: Prepare a saturated aqueous solution of sodium silicate, mix it with a mixture of fine nickel powder, fine tungsten powder and fine praseodymium powder, the molar ratio of Ni:W is 1:0.05 - 1:0.2, the molar ratio of Ni:Pr is 1:0.01 - 1:0.07, and the total weight of the fine nickel powder, fine tungsten powder and fine praseodymium powder is 4 - 8% of the weight of sodium silicate. Adjust to pH 9 - 10 with 5 - 7 mol / L nitric acid under stirring to form a coprecipitate of silica gel and metal fine powder. Separate the coprecipitate of silica gel and metal fine powder by centrifugation, wash the separated coprecipitate with deionized water until neutral, and dry and calcine it for later use.

[0010] Furthermore,

[0011] The drying conditions are: put it in a drying oven and dry at 150 - 180 °C for 4 - 6 hours;

[0012] The calcination conditions are: put it in a muffle furnace and calcine at 500 - 700 °C for 3 - 5 hours.

[0013] Preferably, the specific preparation method of the Zr-Sr-Nd / aluminum hydroxide coprecipitation catalyst is as follows: Adjust the saturated aqueous solution of aluminum trichloride to pH 2 with 5-7 mol / L nitric acid. Dissolve zirconium nitrate, strontium nitrate and neodymium nitrate in water to form a saturated aqueous solution of metal salts. The molar ratio of Zr:Sr is 1:0.2-1:0.4, and the molar ratio of Zr:Nd is 1:0.05-1:0.1. The weights of zirconium nitrate, strontium nitrate and neodymium nitrate in the prepared saturated aqueous solution of metal salts are 5-10% of the weight of aluminum trichloride in the saturated aqueous solution of aluminum trichloride. After mixing the above-prepared solutions, adjust the pH value to 7-8 with a sodium hydroxide solution with a weight concentration of 20-30% to form a precipitate. Separate the precipitate by centrifugation. Wash the separated precipitate with deionized water until neutral, and dry and calcine it for later use.

[0014] Further,

[0015] The drying conditions are as follows: Place it in a drying oven and dry at 150-160 °C for 3-5 hours;

[0016] The calcination conditions are as follows: Place it in a muffle furnace and calcine at 600-800 °C for 4-6 hours.

[0017] Preferably, the hydrogen reduction conditions in step (1) are as follows: Pass in high-purity hydrogen gas for reduction, the reduction temperature is 350-500 °C, and the reduction time is 4-7 hours.

[0018] Preferably, the hydrogenation catalytic conditions in step (2) are as follows: The reaction temperature is 250-450 °C, the reaction pressure is 12-20 MPa, the volume space velocity is 0.6-1.8 h -1 , and the volume ratio of hydrogen to C5 resin is 500:1-800:1.

[0019] Preferably, the pretreatment conditions in step (2) are as follows: Dissolve the C5 resin in cyclohexane or ethyl cyclohexane at a solubility of 10-20 wt%, and filter the solution through a clay or diatomaceous earth filter column.

[0020] Preferably, the surface areas of the Ni-W-Pr / silica gel coprecipitation catalyst and the Zr-Sr-Nd / aluminum hydroxide coprecipitation catalyst are 90-150 square meters per gram, and the catalysts with a pore diameter of 50-100 nm account for 10-20% of the total amount of the catalyst.

[0021] Preferably, the catalytic hydrogenation result of the product is quantitatively analyzed by the internal standard method with a nuclear magnetic resonance spectrometer. The conditions are as follows: The solvent is deuterated chloroform, the sample is 0.1000 g, the internal standard p-nitroacetophenone is 0.0080 g, and the catalytic hydrogenation result is analyzed by the integral area data of the hydrogen absorption peak at 5 ppm on the unsaturated bond of the nuclear magnetic resonance spectrum. Figures 4 - 5 .5 ppm integral area data of the hydrogen absorption peak on the unsaturated bond to analyze the catalytic hydrogenation result.

[0022] Compared with the prior art, the advantages of the present invention are as follows:

[0023] (1) Different catalysts capable of reacting under the same catalytic conditions are placed in the front and rear sections of the fixed bed. The Ni-W-Pr / silica gel catalyst can remove most of the sulfur and halogens in the C5 resin and also has a certain bromine removal effect, while the Zr-Sr-Nd / aluminum hydroxide catalyst mainly functions for deep hydrogenation and can further remove other heteroatoms, and can continue to remove the residual sulfur and nitrogen in the C5 resin. The two different catalysts have different focuses of action, but both can be active under the same conditions and have a complementary effect. The synergistic effect of the two catalysts has achieved a good catalytic effect, simplified the production process, and saved production costs;

[0024] (2) For the Ni-W-Pr / silica gel catalyst prepared by mixing a mixture of fine nickel powder, fine tungsten powder and fine praseodymium powder into silica gel precipitation, the local metal on the catalyst surface is more concentrated and is not easily poisoned, etc.;

[0025] (3) The Zr-Sr-Nd / aluminum hydroxide catalyst is prepared by the precipitation method, so that the metal catalyst is uniformly dispersed on the surface of aluminum hydroxide. The uniformly dispersed metal catalyst is in full contact with the C5 resin, improving the catalytic efficiency while reducing the amount of catalyst used;

[0026] (4) Through the synergistic effect of the Ni-W-Pr / silica gel and Zr-Sr-Nd / aluminum hydroxide catalysts, the bromine value in the C5 resin is reduced from 33.0 gBr / 100 g to below 5.0 gBr / 100 g, the Gardner color is controlled below 4.5, and a high-performance hydrogenated petroleum resin with a softening point above 85 °C, nuclear magnetic resonance spectrum Figures 4 - 5 .5 ppm The integral area of the hydrogen absorption peak on the unsaturated bond decreases, indicating that the catalyst is effective for the catalytic hydrogenation of the C5 resin and improves the analysis speed. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is the nuclear magnetic resonance spectrum of the C5 resin before catalytic hydrogenation in all examples of the present invention;

[0028] Figure 2 is the nuclear magnetic resonance spectrum of the C5 resin after catalytic hydrogenation in Example 1 of the present invention;

[0029] Figure 3 is the nuclear magnetic resonance spectrum of the C5 resin after catalytic hydrogenation in Example 2 of the present invention;

[0030] Figure 4 is the nuclear magnetic resonance spectrum of the C5 resin after catalytic hydrogenation in Example 3 of the present invention;

[0031] Figure 51H NMR spectrum of the C5 resin after catalytic hydrogenation in Example 4 of the present invention;

[0032] Figure 6 1H NMR spectrum of the C5 resin after catalytic hydrogenation in Example 5 of the present invention. Detailed implementation mode

[0033] The present invention will be further described in detail below in conjunction with the embodiments and the drawings.

[0034] Example 1:

[0035] (1) A Ni-W-Pr / silica co-precipitation catalyst is placed in the first half of the fixed bed, and a Zr-Sr-Nd / aluminum hydroxide co-precipitation catalyst is placed in the second half of the fixed bed. The hydrogen reduction conditions are as follows: introducing 99.999% high-purity hydrogen gas for reduction, the reduction temperature is 350 °C, and the reduction time is 4 hours;

[0036] Among them, the preparation of the Ni-W-Pr / silica co-precipitation catalyst includes the following steps: preparing a saturated sodium silicate solution, mixing a mixture of fine nickel powder, fine tungsten powder and fine praseodymium powder, the molar ratio of Ni:W is 1:0.05, the molar ratio of Ni:Pr is 1:0.01, and the total weight of the fine nickel powder, fine tungsten powder and fine praseodymium powder is 4% of the weight of sodium silicate. Adjust to pH 9 with 7 mol / L nitric acid under electric stirring (400 revolutions per minute) to form a co-precipitation of silica and metal fine powder. Separate the co-precipitation of silica and metal fine powder by centrifugation, wash the separated co-precipitation with deionized water until neutral, dry the co-precipitation at 180 °C for 4 hours, and calcine the dried co-precipitation in a muffle furnace at 500 °C for 5 hours;

[0037] Among them, the preparation of the Zr-Sr-Nd / aluminum hydroxide co-precipitation catalyst: adjust the saturated aluminum chloride solution to pH 2 with 5 mol / L nitric acid, prepare saturated aqueous solutions of zirconium nitrate, strontium nitrate and neodymium nitrate, the molar ratio of Zr:Sr is 1:0.2, the molar ratio of Zr:Nd is 1:0.05, and the weights of zirconium nitrate, strontium nitrate and neodymium nitrate in the prepared solution are 5% of the weight of aluminum chloride. Mix the prepared above solutions and adjust to pH 7 with a 20% by weight sodium hydroxide solution to form a precipitate. Separate the precipitate by centrifugation, wash the separated precipitate with deionized water until neutral, dry the precipitate at 150 °C for 3 hours, and calcine the dried precipitate in a muffle furnace at 600 °C for 6 hours;

[0038] (2) Dissolve the C5 resin in cyclohexane or ethyl cyclohexane at a solubility of 20 wt%, pass the solution through a clay or diatomaceous earth filter column, and the pretreated C5 resin solution enters catalytic hydrogenation. The catalytic hydrogenation conditions are: reaction temperature 250 °C, reaction pressure 12 MPa, volumetric space velocity 1.8 h -1The volume ratio of hydrogen to C5 resin is 800:1.

[0039] The catalytic hydrogenation results of the product were quantitatively analyzed by the internal standard method using a nuclear magnetic resonance spectrometer. The conditions were as follows: deuterated chloroform as the solvent, 0.1000 g of the sample, and 0.0080 g of p-nitroacetophenone as the internal standard. The catalytic hydrogenation results were analyzed using the integral area data of the hydrogen absorption peaks on the unsaturated bonds at Figures 4 - 5 5 ppm. The same applies hereinafter.

[0040] The nuclear magnetic resonance spectrum of the C5 resin before catalytic hydrogenation is as shown in Figure 1 and the nuclear magnetic resonance spectrum of the C5 resin after catalytic hydrogenation in this example is as shown in Figure 2 .

[0041] It can be seen from Figure 2 that the integral area of the hydrogen absorption peaks on the unsaturated bonds at 4 - Figure 1 5.5 ppm decreased from 4.46 to 0.99. The bromine value of the C5 resin decreased from 33 gBr / 100 g to 5.0 gBr / 100 g, and the Gardner color number was 4.5, achieving a good bromine removal effect, indicating that the catalyst is effective for the catalytic hydrogenation of C5 resin.

[0042] Example 2:

[0043] (1) A Ni-W-Pr / silica gel coprecipitation catalyst was placed in the first half of the fixed bed, and a Zr-Sr-Nd / aluminum hydroxide coprecipitation catalyst was placed in the second half of the fixed bed. The hydrogen reduction conditions were as follows: reduction was carried out by introducing 99.999% high-purity hydrogen gas, the reduction temperature was 400 °C, and the reduction time was 5 hours;

[0044] The preparation of the Ni-W-Pr / silica gel coprecipitation catalyst included the following steps: preparing a saturated sodium silicate solution, mixing a mixture of fine nickel powder, fine tungsten powder, and fine praseodymium powder, with the molar ratio of Ni:W being 1:0.15 and the molar ratio of Ni:Pr being 1:0.06. The total weight of the fine nickel powder, fine tungsten powder, and fine praseodymium powder was 7% of the weight of sodium silicate. It was adjusted to pH 10 with 6 mol / L nitric acid under electric stirring (at 500 revolutions per minute) to form a coprecipitation of silica gel and metal fine powder. The coprecipitate of silica gel and metal fine powder was separated by centrifugation, and the separated coprecipitate was washed with deionized water until neutral. The coprecipitate was dried at 160 °C for 5 hours, and the dried coprecipitate was calcined in a muffle furnace at 600 °C for 5 hours;

[0045] Among them, the preparation of the Zr-Sr-Nd / aluminum hydroxide coprecipitation catalyst: Adjust the saturated aluminum chloride solution to a pH value of 1 with 6 mol / L nitric acid, prepare saturated aqueous solutions of zirconium nitrate, strontium nitrate, and neodymium nitrate, with a Zr:Sr molar ratio of 1:0.3 and a Zr:Nd molar ratio of 1:0.09. The weights of zirconium nitrate, strontium nitrate, and neodymium nitrate in the prepared solution are 7% of the weight of aluminum chloride. After mixing the prepared above solutions, adjust the pH value to 7 with a 30% sodium hydroxide solution by weight to form a precipitate. The precipitate is separated by centrifugation, and the separated precipitate is washed with deionized water until neutral. The precipitate is dried at 150 °C for 4 hours, and the dried precipitate is calcined in a muffle furnace at 700 °C for 5 hours;

[0046] (2) Dissolve the C5 resin in cyclohexane or ethyl cyclohexane at a solubility of 11 wt%, and the solution is filtered through a clay or diatomaceous earth filter column. The pretreated C5 resin solution enters catalytic hydrogenation. The catalytic hydrogenation conditions are: reaction temperature 300 °C, reaction pressure 16 MPa, volume space velocity 1.2 h -1 , and the volume ratio of hydrogen to C5 resin is 600:1.

[0047] In this example, the nuclear magnetic resonance spectrum of the C5 resin after catalytic hydrogenation is as Figure 3 shown.

[0048] From Figure 3 it can be seen that the integral area of the hydrogen absorption peak on the unsaturated bond at 4 - 5.5 ppm decreases from Figure 1 4.46 to 0.42. The bromine number of the C5 resin decreases from 33 gBr / 100 g to 3.2 gBr / 100 g, and the Gardner color number is 1.5, achieving a good bromine removal effect, indicating that the catalyst is effective for the catalytic hydrogenation of the C5 resin.

[0049] Example 3:

[0050] (1) Place the Ni-W-Pr / silica coprecipitation catalyst in the first half of the fixed bed and the Zr-Sr-Nd / aluminum hydroxide coprecipitation catalyst in the second half of the fixed bed. The hydrogen reduction conditions are: reducing with 99.999% high-purity hydrogen gas, reduction temperature 450 °C, and reduction time 6 hours;

[0051] Among them, the preparation of the Ni-W-Pr / silica co-precipitation catalyst includes the following steps: Prepare a saturated sodium silicate solution, mix in a mixture of fine nickel powder, fine tungsten powder, and fine praseodymium powder. The molar ratio of Ni:W is 1:0.08, and the molar ratio of Ni:Pr is 1:0.05. The total weight of the fine nickel powder, fine tungsten powder, and fine praseodymium powder is 5% of the weight of sodium silicate. While stirring electrically (at a speed of 600 revolutions per minute), adjust to a pH value of 10 with 5 mol / L nitric acid to form a co-precipitation of silica and metal fine powder. Separate the co-precipitate of silica and metal fine powder by centrifugation. Wash the separated co-precipitate with deionized water until neutral. Dry the co-precipitate at 170°C for 5 hours. Calcinate the dried co-precipitate in a muffle furnace at 600°C for 4 hours;

[0052] Among them, the preparation of the Zr-Sr-Nd / aluminum hydroxide co-precipitation catalyst: Adjust the saturated aluminum chloride solution to a pH value of 2 with 6 mol / L nitric acid. Prepare saturated aqueous solutions of zirconium nitrate, strontium nitrate, and neodymium nitrate. The molar ratio of Zr:Sr is 1:0.25, and the molar ratio of Zr:Nd is 1:0.08. The weights of zirconium nitrate, strontium nitrate, and neodymium nitrate in the prepared solution are 8% of the weight of aluminum chloride. After mixing the prepared above solutions, adjust to a pH value of 8 with a 20% by weight sodium hydroxide solution to form a precipitate. Separate the precipitate by centrifugation. Wash the separated precipitate with deionized water until neutral. Dry the precipitate at 150°C for 5 hours. Calcinate the dried precipitate in a muffle furnace at 650 - 800°C for 5 hours;

[0053] (2) Dissolve the C5 resin in cyclohexane or ethyl cyclohexane at a solubility of 5 wt%. Pass the solution through a clay or diatomaceous earth filter column. The pretreated C5 resin solution enters catalytic hydrogenation. The conditions for catalytic hydrogenation are: reaction temperature 350°C, reaction pressure 14 MPa, volume space velocity 1.3 h -1 , and the volume ratio of hydrogen to C5 resin is 700:1.

[0054] In this example, the nuclear magnetic resonance spectrum of the C5 resin after catalytic hydrogenation is as Figure 4 shown.

[0055] From Figure 4 it can be seen that the integral area of the hydrogen absorption peak on the unsaturated bond at 4 - 5.5 ppm decreases from Figure 1 4.46 to 0.38. The bromine number of the C5 resin drops from 33 gBr / 100 g to 2.5 gBr / 100 g, and the Gardner color number is 1.2, achieving a good bromine removal effect, indicating that the catalyst is effective for the catalytic hydrogenation of the C5 resin.

[0056] Example 4:

[0057] (1) Place the Ni-W-Pr / silica co-precipitation catalyst in the first half of the fixed bed and the Zr-Sr-Nd / aluminum hydroxide co-precipitation catalyst in the second half of the fixed bed. The hydrogen reduction conditions are as follows: Introduce 99.999% high-purity hydrogen gas for reduction, the reduction temperature is 450 °C, and the reduction time is 7 hours;

[0058] Among them, the preparation of the Ni-W-Pr / silica co-precipitation catalyst includes the following steps: Prepare a saturated sodium silicate solution, mix it with a mixture of fine nickel powder, fine tungsten powder and fine praseodymium powder. The molar ratio of Ni:W is 1:0.1, and the molar ratio of Ni:Pr is 1:0.03. The total weight of the fine nickel powder, fine tungsten powder and fine praseodymium powder is 6% of the weight of sodium silicate. Adjust to pH 9 with 6 mol / L nitric acid under electric stirring (550 revolutions per minute) to form a co-precipitation of silica and metal fine powder. Separate the co-precipitation of silica and metal fine powder by centrifugation, wash the separated co-precipitation with deionized water until neutral, dry the co-precipitation at 160 °C for 5 hours, and calcine the dried co-precipitation in a muffle furnace at 700 °C for 5 hours;

[0059] Among them, the preparation of the Zr-Sr-Nd / aluminum hydroxide co-precipitation catalyst includes the following steps: Adjust the saturated aluminum chloride solution to pH 2 with 6 mol / L nitric acid, prepare saturated aqueous solutions of zirconium nitrate, strontium nitrate and neodymium nitrate. The molar ratio of Zr:Sr is 1:0.3, and the molar ratio of Zr:Nd is 1:0.07. The weights of zirconium nitrate, strontium nitrate and neodymium nitrate in the prepared solution are 7% of the weight of aluminum chloride. Mix the prepared above solutions and adjust to pH 7 with a 30% sodium hydroxide solution by weight to form a precipitate. Separate the precipitate by centrifugation, wash the separated precipitate with deionized water until neutral, dry the precipitate at 150 °C for 4 hours, and calcine the dried precipitate in a muffle furnace at 700 °C for 5 hours;

[0060] (2) Dissolve the C5 resin in cyclohexane or ethyl cyclohexane at a solubility of 8 wt%, and pass the solution through a clay or diatomaceous earth filter column. The pretreated C5 resin solution enters catalytic hydrogenation. The catalytic hydrogenation conditions are as follows: reaction temperature 400 °C, reaction pressure 18 MPa, volumetric space velocity 1.0 h -1 , and the volume ratio of hydrogen to C5 resin is 800:1.

[0061] In this example, the nuclear magnetic resonance spectrum of the C5 resin after catalytic hydrogenation is as Figure 5 shown.

[0062] From Figure 5 it can be seen that the integral area of the hydrogen absorption peak on the unsaturated bond at 4 - 5.5 ppm changes from Figure 1It decreased from 4.46 to 0.05, the bromine value of the C5 resin dropped from 33 gBr / 100 g to 0.9 gBr / 100 g, and the Gardner color number was 0.5, achieving a good bromine removal effect, indicating that the catalyst is effective for the catalytic hydrogenation of C5 resin.

[0063] Example 5:

[0064] (1) Put the Ni-W-Pr / silica gel coprecipitation catalyst in the first half of the fixed bed, and put the Zr-Sr-Nd / aluminum hydroxide coprecipitation catalyst in the second half of the fixed bed. The hydrogen reduction conditions are: reducing with 99.999% high-purity hydrogen gas, the reduction temperature is 500 °C, and the reduction time is 7 hours;

[0065] Among them, the preparation of the Ni-W-Pr / silica gel coprecipitation catalyst includes the following steps: Prepare a saturated sodium silicate solution, mix in a mixture of fine nickel powder, fine tungsten powder and fine praseodymium powder. The molar ratio of Ni:W is 1:0.2, and the molar ratio of Ni:Pr is 1:0.07. The total weight of the fine nickel powder, fine tungsten powder and fine praseodymium powder is 8% of the weight of sodium silicate. Adjust to pH 10 with 5 mol / L nitric acid under electric stirring (450 revolutions per minute) to form a coprecipitation of silica gel and metal fine powder. Separate the coprecipitation of silica gel and metal fine powder by centrifugation, wash the separated coprecipitation with deionized water until neutral, dry the coprecipitation at 150 °C for 6 hours, and calcine the dried coprecipitation in a muffle furnace at 700 °C for 3 hours;

[0066] Among them, the preparation of the Zr-Sr-Nd / aluminum hydroxide coprecipitation catalyst: Adjust the saturated aluminum chloride solution to pH 1 with 7 mol / L nitric acid, prepare saturated aqueous solutions of zirconium nitrate, strontium nitrate and neodymium nitrate. The molar ratio of Zr:Sr is 1:0.4, and the molar ratio of Zr:Nd is 1:0.1. The weights of zirconium nitrate, strontium nitrate and neodymium nitrate in the prepared solution are 10% of the weight of aluminum chloride. Mix the prepared above solutions and adjust to pH 8 with a 30% sodium hydroxide solution by weight to form a precipitate. Separate the precipitate by centrifugation, wash the separated precipitate with deionized water until neutral, dry the precipitate at 160 °C for 5 hours, and calcine the dried precipitate in a muffle furnace at 800 °C for 4 hours;

[0067] (2) Dissolve the C5 resin in cyclohexane or ethylcyclohexane at a solubility of 15 wt%, pass the solution through a filter column of clay or diatomaceous earth, and the pretreated C5 resin solution enters catalytic hydrogenation. The catalytic hydrogenation conditions are: reaction temperature 450 °C, reaction pressure 20 MPa, volume space velocity 1.6 h -1 -1, and the volume ratio of hydrogen to C5 resin is 500:1.

[0068] The nuclear magnetic resonance spectrum of the C5 resin after catalytic hydrogenation in this example is as Figure 6 shown.

[0069] From Figure 6 it can be seen that the integral area of the hydrogen absorption peak on the unsaturated bond at 4 - 5.5 ppm decreases from Figure 1 4.46 to 0.65, the bromine number of the C5 resin drops from 33 gBr / 100 g to 3.5 gBr / 100 g, and the Gardner color number is 2.3, achieving a good bromine removal effect, indicating that the catalyst is effective for the catalytic hydrogenation of C5 resin.

Claims

1. A catalytic hydrogenation method for C5 resin, characterized in that it includes the following steps: (1) Place the Ni-W-Pr / silica gel coprecipitation catalyst in the first half of the fixed bed, and place the Zr-Sr-Nd / aluminum hydroxide coprecipitation catalyst in the second half of the fixed bed, and introduce hydrogen for reduction; (2) Catalytically hydrogenate the pretreated C5 resin in the fixed bed; The specific preparation method of the Ni-W-Pr / silica gel coprecipitation catalyst is as follows: Prepare a saturated aqueous solution of sodium silicate, mix in a mixture of fine nickel powder, fine tungsten powder and fine praseodymium powder, the molar ratio of Ni:W is 1:0.05 to 1:0.2, the molar ratio of Ni:Pr is 1:0.01 to 1:0.07, and the total weight of the fine nickel powder, fine tungsten powder and fine praseodymium powder is 4 to 8% of the weight of sodium silicate. Adjust to pH 9-10 with 5-7 mol / L nitric acid under stirring to form a coprecipitate of silica gel and metal fine powder. Separate the coprecipitate of silica gel and metal fine powder by centrifugation. Wash the separated coprecipitate with deionized water until neutral, and dry and calcine for later use; The specific preparation method of the Zr-Sr-Nd / aluminum hydroxide coprecipitation catalyst is as follows: Adjust the saturated aqueous solution of aluminum trichloride to pH 2 with 5-7 mol / L nitric acid. Dissolve zirconium nitrate, strontium nitrate and neodymium nitrate in water to prepare a saturated aqueous solution of metal salts. The molar ratio of Zr:Sr is 1:0.2 to 1:0.4, the molar ratio of Zr:Nd is 1:0.05 to 1:0.

1. The weight of zirconium nitrate, strontium nitrate and neodymium nitrate in the prepared saturated aqueous solution of metal salts is 5 to 10% of the weight of aluminum trichloride in the saturated aqueous solution of aluminum trichloride. Mix the above-prepared solutions and adjust to pH 7-8 with a 20-30% sodium hydroxide solution by weight to form a precipitate. Separate the precipitate by centrifugation. Wash the separated precipitate with deionized water until neutral, and dry and calcine for later use.

2. The catalytic hydrogenation method for C5 resin according to claim 1, characterized in that: The drying conditions are: place in a drying oven and dry at 150-180°C for 4-6 hours; The calcination conditions are: place in a muffle furnace and calcine at 500-700°C for 3-5 hours.

3. The catalytic hydrogenation method for C5 resin according to claim 1, characterized in that: The drying conditions are: place in a drying oven and dry at 150-160°C for 3-5 hours; The calcination conditions are: place in a muffle furnace and calcine at 600-800°C for 4-6 hours.

4. The catalytic hydrogenation method for C5 resin according to any one of claims 1 to 3, characterized in that: The hydrogen reduction conditions in step (1) are: introduce high-purity hydrogen gas for reduction, the reduction temperature is 350-500°C, and the reduction time is 4-7 hours.

5. The catalytic hydrogenation method for C5 resin according to any one of claims 1 to 3, characterized in that: The hydrogenation catalytic conditions described in step (2) are as follows: reaction temperature 250-450 °C, reaction pressure 12-20 MPa, volumetric space velocity 0.6-1.8 h -1 , and the volume ratio of hydrogen to C5 resin is 500:1-800:

1.

6. The catalytic hydrogenation method for C5 resin according to any one of claims 1 to 3, characterized in that: The pretreatment conditions described in step (2) are as follows: dissolve the C5 resin in cyclohexane or ethyl cyclohexane at a solubility of 10-20 wt%, and filter the solution through a filter column of clay or diatomaceous earth.

7. The catalytic hydrogenation method of the C5 resin according to any one of claims 1 to 3, characterized in that: the surface areas of the Ni-W-Pr / silica gel coprecipitation catalyst and the Zr-Sr-Nd / aluminum hydroxide coprecipitation catalyst are 90-150 m2 / g, and the catalysts with a pore diameter of 50-100 nm account for 10-20% of the total amount of the catalyst.

8. The catalytic hydrogenation method of the C5 resin according to any one of claims 1 to 3, characterized in that: the catalytic hydrogenation result of the product is quantitatively analyzed by the internal standard method using a nuclear magnetic resonance spectrometer. The conditions are as follows: deuterated chloroform as the solvent, 0.1000 g of the sample, 0.0080 g of p-nitroacetophenone as the internal standard, and the catalytic hydrogenation result is analyzed by the integral area data of the hydrogen absorption peak on the unsaturated bond at 4-5.5 ppm in the nuclear magnetic resonance spectrum.

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