JP7079380B2 - Contact hydrogenation method for C9 resin - Google Patents

Description

The present invention relates to catalytic hydrogenation of petroleum resin, and more particularly to a method of catalytic hydrogenation of C9 resin.

The C9 resin is a by-product obtained when ethylene is produced by decomposition. The catalytic hydrogenation of the C9 resin saturates the double bonds and some benzene rings in the resin and desorbs the halogen elements remaining in the resin polymerization process, resulting in resin chromaticity, photothermal stability, and oxidation stability. It can improve the properties and UV resistance, improve the product quality, and expand the applications. With the development of adhesives and sealants, the color is lighter, especially for transparent pressure sensitive tapes, outdoor sealants, disposable hygiene products, medical tapes, traffic paints, polyolefin modifiers. Petroleum resin that has no odor and has good stability is required, and one of them is C9 resin. For this reason, the market demand for hydrogenated C9 resin is increasing rapidly, and the development of contact hydrogenation technology for C9 resin is also progressing, but the key that influences the quality of the product after hydrogenation of C9 resin is. It is in the selection of catalyst.

The raw material component of the C9 resin is complicated (usually, there are many impurities such as color-developing groups, gels, S, and Cl). Resin hydrogenation catalysts are mainly divided into two types of catalysts, precious metals and non-precious metals. Precious metal catalysts are mainly palladium-based and palladium-platinum-based catalysts, and these catalysts have the advantages of high activity, low starting temperature, high yield, and good quality, but are poisoned by sulfur and the like. It is sensitive to substances and has the disadvantage of being extremely poisonous and easily deactivated. Non-precious metal catalysts are mainly nickel-based catalysts, nickel-tungsten-based or nickel sulfide-molybdenum-based catalysts supported on diatomaceous soil or alumina-diatomaceous soil, and although this type of catalyst has high sulfur resistance, these catalysts Disadvantages are high catalytic activity, still high bromine value of the product, remarkable hydrocracking, product resin yield of only about 80%, softening point from 120 ° C to 90 ° C. It is reduced and the catalyst life is short. For this reason, in the prior art, different catalysts were used and the C9 resin was catalytically hydrogenated in multiple stages.

In the Chinese patent CN102924659A, the first-stage catalyst is mainly Ni / Al ₂ O3 for removing sulfur in the raw material resin, and the _second -stage catalyst is mainly a noble metal for hydrogenation decolorization treatment. A method for hydrogenating a resin using a two-stage fixed bed, which is a Pt-Pd / Al ₂ O ₃ hydrogenation catalyst, is disclosed. In this, the hydrogenation reaction pressure of the first stage hydrogenation desulfurization is 2.0 to 6.0 MPa, the reaction temperature is 250 to 350 ° C., the liquid spatiotemporal space velocity is 1 to 5 h ^-1 , and the second stage hydrogen. The decolorization hydrogenation reaction pressure is 6.0 to 12.0 MPa, the reaction temperature is 250 to 350 ° C., the liquid spatiotemporal space velocity is 1 to 5 h ^-1 , and the high-pressure contact hydrogenation treatment of the fixed floor is adopted. There is. This method takes full advantage of the two-stage catalyst to improve the life of the noble metal catalyst. However, the disadvantages are that there is still room for improvement in terms of catalytic activity _, and because _Al2O3 is used as a carrier, the dispersion of the catalyst on the carrier becomes non-uniform and the catalytic reaction effect is inferior. Since the catalyst adopts different pressurizing conditions, it cannot be completed on the same fixed bed, the production efficiency is low, and there is pressure interference in the actual operation process, which affects the quality of the final C9 resin. Can be mentioned.

To summarize the above, at present, the hydrogenation catalyst of C9 resin has problems such as non-uniform dispersion of the catalyst on the carrier and inferior catalytic reaction effect. Therefore, there is a need for the development of a catalytic hydrogenation method for C9 resin, which has high catalytic efficiency and a simple process.

An object to be solved by the present invention is to provide a method for catalytic hydrogenation of a C9 resin having a good chromaticity, a low bromine value, and a simple process, as opposed to the current state of the prior art.

The means adopted by the present invention to solve the above-mentioned technical problems are as follows.

In the present invention, 1) a Zr-Mo-Y / silica gel co-precipitation catalyst is placed in the first half of the fixed bed, a Ni-Nd-Gd / silica gel co-precipitation catalyst is placed in the second half of the fixed bed, and hydrogen gas is introduced for reduction. 2) A method for catalytic hydrogenation of C9 resin, which comprises contact hydrogenating the pretreated C9 resin in a fixed bed.

Preferably, for the preparation of the Zr-Mo-Y / silica gel co-precipitation catalyst, the saturated sodium silicate solution is adjusted to pH 1 to 2 with 5 to 7 mol / L nitrate, and the molar ratio of Zr: Mo is 1: 0.1. Aqueous solution of zirconium nitrate, molybdenum nitrate and yttrium nitrate having a molar ratio of ~ 1: 0.5 and Zr: Y of 1: 0.05 to 1: 0.3 is added, and zirconium nitrate and nitrate in the prepared solution are added. The weight of molybdenum and yttrium nitrate should be 5-10% of the weight of sodium silicate, the prepared solution should be adjusted to pH 9-10 with saturated aqueous sodium carbonate solution to form a precipitate, and the precipitate should be separated and separated by centrifugation. The resulting precipitate is washed with deionized water until neutral, then the precipitate is dried at 100-150 ° C for 3-5 hours, and the dried precipitate is placed in a muffle furnace at 500-700 ° C for 3-5. Including the step of baking for hours
To prepare a Ni-Nd-Gd / silica gel co-precipitation catalyst, adjust the pH of a saturated sodium silicate solution to 1 to 2 with 5 to 7 mol / L nitrate, and the molar ratio of Ni: Nd is 1: 0.03 to 1: 1. An aqueous solution of nickel nitrate, neodymite nitrate and gadrinium nitrate having a molar ratio of 0.1 and Ni: Gd of 1: 0.01 to 1: 0.08 was added to the prepared solution, and nickel nitrate, neodymite nitrate and nitrate were added. The weight of gadrinium is adjusted to 5 to 10% of the weight of sodium silicate, the prepared solution is adjusted to pH 9 to 10 with a saturated sodium carbonate solution to form a precipitate, and the precipitate is separated by centrifugation and the separated precipitate. Is washed with deionized water until neutral, then the solution is dried at 100-150 ° C. for 3-5 hours, and the dried solution is baked in a muffle furnace at 500-700 ° C. for 3-5 hours. Including steps.

Preferably, the hydrogen gas reduction conditions of the Zr-Mo-Y / silica gel coprecipitation catalyst and the Ni-Nd-Gd / silica gel coprecipitation catalyst are such that a high-purity hydrogen gas is introduced, the reduction temperature is 350 to 500 ° C., and the reduction time. It is to reduce in 5 to 10 hours.

Preferably, the conditions for catalytic hydrogenation are a reaction temperature of 250 to 450 ° C., a reaction pressure of 10 to 25 MPa, a volumetric space velocity of 0.1 to 1.0 h ^-1 , and a volume ratio of hydrogen to C9 resin of 400: 1. ~ 900: 1.

Preferably, the pretreatment condition for the C9 resin is to dissolve the C9 resin with cyclohexane or ethylcyclohexane at a solubility of 5-20 wt% and pass the solution through a filtration column of white clay or diatomaceous earth.

Preferably, the Zr-Mo-Y / silica gel co-precipitation catalyst and the Ni-Nd-Gd / silica gel co-precipitation catalyst have a surface area of 90 to 150 m ² / g and a pore size of 50 to 100 nm occupying 10 to 20%.

The advantages of the present invention over the prior art are as follows.

1) Different catalysts capable of reacting under the same catalytic reaction conditions are placed in the front and rear stages of the fixed bed. The Zr-Mo-Y / silica gel catalyst can desorb most of the sulfur and halogen elements in the C9 resin, and also has a certain bromine removing effect. On the other hand, the Ni-Nd-Gd / silica gel catalyst mainly has the action of high hydrogenation and also has the action of desorbing other heteroatoms, so that sulfur and nitrogen remaining in the C9 resin should be continuously removed. Can be done. Although the emphasis of the action of the two different catalysts is different, both can exert their activity under the same conditions and have complementary actions, so that the synergistic action of the two catalysts is good. A catalyst reaction effect can be obtained, the production process can be simplified, and the production cost can be reduced.

2) By producing the Zr-Mo-Y / silica gel catalyst and the Ni-Nd-Gd / silica gel catalyst by the precipitation method, the metal catalyst can be uniformly dispersed on the surface of the silica gel. The surface area of the co-precipitation catalyst is 90 to 150 m ² / g, the pore size of 50 to 100 nm occupies 10 to 20%, and the uniformly dispersed metal catalyst sufficiently contacts the C9 resin, so that the amount of the catalyst used is reduced. At the same time, the catalytic reaction efficiency is improved.

3) The synergistic action of the Zr-Mo-Y / silica gel catalyst and the Ni-Nd-Gd / silica gel catalyst reduces the bromine value in the C9 resin from 32.5 gBr / 100 g to 6.0 g Br / 100 g or less, and reduces the number of Gardner colors. It can be suppressed to 6.0 or less. This indicates that the catalyst is effective for catalytic hydrogenation of the C9 resin.

It is an infrared spectrum before the catalytic hydrogenation of the C9 resin of Example 1 of this invention. It is an infrared spectrum after the catalytic hydrogenation of the C9 resin of Example 1 of this invention. It is an infrared spectrum before the catalytic hydrogenation of the C9 resin of Example 2 of this invention. It is an infrared spectrum after the catalytic hydrogenation of the C9 resin of Example 2 of this invention. It is an infrared spectrum before the catalytic hydrogenation of the C9 resin of Example 3 of this invention. 6 is an infrared spectrum of the C9 resin of Example 3 of the present invention after catalytic hydrogenation. It is an infrared spectrum before the catalytic hydrogenation of the C9 resin of Example 4 of this invention. 6 is an infrared spectrum of the C9 resin of Example 4 of the present invention after catalytic hydrogenation. It is an infrared spectrum before the catalytic hydrogenation of the C9 resin of Example 5 of this invention. 6 is an infrared spectrum of the C9 resin of Example 5 of the present invention after catalytic hydrogenation.

Hereinafter, specific embodiments of the present invention will be described in more detail with reference to the drawings and examples.

The method for catalytic hydrogenation of C9 resin includes the following steps 1 and 2.

Step 1) Put the Zr-Mo-Y / silica gel co-precipitation catalyst in the first half of the fixed bed, put the Ni-Nd-Gd / silica gel co-precipitation catalyst in the second half of the fixed bed, and put the high purity of 99.9999% in the fixed bed. Hydrogen gas is introduced and reduced at a reduction temperature of 350 ° C. and a reduction time of 10 hours.

Here, the preparation of the Zr-Mo-Y / silica gel coprecipitation catalyst includes the following steps. The saturated sodium silicate solution is adjusted to pH 1 with 6 mol / L nitric acid, and zirconium nitrate, molybdenum nitrate and molybdenum nitrate having a Zr: Mo molar ratio of 1: 0.1 and a Zr: Y molar ratio of 1: 0.3. Add an aqueous solution of yttrium nitrate. The weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution is 5% by weight of sodium silicate. Then, the prepared solution is adjusted to pH 9 with a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by a centrifugation method, the separated precipitate is washed with deionized water until it becomes neutral, and then the precipitate is settled. The product is dried at 125 ° C. for 4 hours, and the dried precipitate is fired at 500 ° C. for 3 hours in a muffle furnace.

Here, the preparation of the Ni-Nd-Gd / silica gel coprecipitation catalyst includes the following steps. The saturated sodium silicate solution is adjusted to pH 2 with 6 mol / L nitrate, and nickel nitrate, neodymium nitrate and Ni: Nd having a molar ratio of 1: 0.1 and Ni: Gd having a molar ratio of 1: 0.01. Add an aqueous solution of gadolinium nitrate. The weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 10% by weight of sodium silicate. Then, the prepared solution is adjusted to pH 10 with a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by a centrifugation method, the separated precipitate is washed with deionized water until it becomes neutral, and then the precipitate is settled. The product is dried at 125 ° C. for 4 hours, and the dried precipitate is fired at 700 ° C. for 5 hours in a muffle furnace.

Step 2) The pretreated C9 resin is catalytically hydrogenated in a fixed floor.

The C9 resin is dissolved with cyclohexane at a solubility of 5 wt% and the solution is passed through a filtration column of white clay to adsorb insoluble gels, asphaltene and small amounts of free heavy metals onto the white clay. Then, the pretreated C9 resin solution is catalytically hydrogenated.

The conditions for catalytic hydrogenation are a reaction temperature of 450 ° C., a reaction pressure of 10 MPa, a volumetric space velocity of 0.1 h ^-1 , and a volume ratio of hydrogen to C9 resin of 400: 1.

As can be seen from FIG. 2, the absorption peak of the carbon-hydrogen bond on the carbon ^- carbon double bond at 3041 cm-1 is the absorption of the carbon-hydrogen bond on the carbon-carbon double bond at 3041 cm ^-1 in FIG. Significantly smaller than the peak. Further, the bromine value of the C9 resin is lowered from 34 gBr / 100 g to 3.2 g Br / 100 g, and the number of Gardner colors is 3.2. This indicates that the catalyst is effective for catalytic hydrogenation of the C9 resin.

The method for catalytic hydrogenation of C9 resin includes the following steps 1 and 2.

Step 1) Put the Zr-Mo-Y / silica gel co-precipitation catalyst in the first half of the fixed bed, put the Ni-Nd-Gd / silica gel co-precipitation catalyst in the second half of the fixed bed, and put the high purity of 99.9999% in the fixed bed. Including the step of introducing the hydrogen gas of the above and reducing it at a reduction temperature of 500 ° C. and a reduction time of 5 hours.

Here, the preparation of the Zr-Mo-Y / silica gel coprecipitation catalyst includes the following steps. The saturated sodium silicate solution is adjusted to pH 2 with 6 mol / L nitric acid, and zirconium nitrate, molybdenum nitrate and molybdenum nitrate having a Zr: Mo molar ratio of 1: 0.5 and a Zr: Y molar ratio of 1: 0.05. Add an aqueous solution of yttrium nitrate. The weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution is 10% by weight of sodium silicate. Then, the prepared solution is adjusted to pH 10 with a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by a centrifugation method, the separated precipitate is washed with deionized water until it becomes neutral, and then the precipitate is settled. The product is dried at 125 ° C. for 4 hours, and the dried precipitate is fired at 700 ° C. for 5 hours in a muffle furnace.

Here, the preparation of the Ni-Nd-Gd / silica gel coprecipitation catalyst includes the following steps. The saturated sodium silicate solution is adjusted to pH 1 with 6 mol / L nitrate, and nickel nitrate, neodymium nitrate and Ni: Nd having a molar ratio of 1: 0.03 and Ni: Gd having a molar ratio of 1: 0.08. Add an aqueous solution of gadolinium nitrate. The weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 5% by weight of sodium silicate. Then, the prepared solution is adjusted to pH 9 with a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by a centrifugation method, the separated precipitate is washed with deionized water until it becomes neutral, and then the precipitate is settled. The product is dried at 125 ° C. for 4 hours, and the dried precipitate is fired at 500 ° C. for 3 hours in a muffle furnace.

Step 2) The pretreated C9 resin is catalytically hydrogenated in a fixed floor.

The C9 resin is dissolved with ethylcyclohexane at a solubility of 20 wt% and the solution is passed through a filtration column of white clay to adsorb insoluble gel, asphaltene and a small amount of free heavy metals on the white clay. Then, the pretreated C9 resin solution is catalytically hydrogenated.

The conditions for catalytic hydrogenation are a reaction temperature of 250 ° C., a reaction pressure of 25 MPa, a volumetric space velocity of 1.0 h ^-1 , and a volume ratio of hydrogen to C9 resin of 900: 1.

As can be seen from FIG. 4, the absorption peak of the carbon-hydrogen bond on the carbon ^- carbon double bond at 3041 cm ^-1 is the absorption of the carbon-hydrogen bond on the carbon-carbon double bond at 3041 cm-1 in FIG. Significantly smaller than the peak. Further, the bromine value of the C9 resin is lowered from 34 gBr / 100 g to 5.3 g Br / 100 g, and the number of Gardner colors is 5.9. This indicates that the catalyst is effective for catalytic hydrogenation of the C9 resin.

The method for catalytic hydrogenation of C9 resin includes the following steps 1 and 2.

Step 1) Put the Zr-Mo-Y / silica gel co-precipitation catalyst in the first half of the fixed bed, put the Ni-Nd-Gd / silica gel co-precipitation catalyst in the second half of the fixed bed, and put the high purity of 99.9999% in the fixed bed. Hydrogen gas is introduced and reduced at a reduction temperature of 400 ° C. and a reduction time of 7 hours.

Here, the preparation of the Zr-Mo-Y / silica gel coprecipitation catalyst includes the following steps. The saturated sodium silicate solution is adjusted to pH 1.5 with 6 mol / L nitric acid, and the molar ratio of Zr: Mo is 1: 0.2 and the molar ratio of Zr: Y is 1: 0.1. Add an aqueous solution of molybdenum and yttrium nitrate. The weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution is 7% by weight of sodium silicate. Then, the prepared solution is adjusted to pH 9.5 with a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by a centrifugation method, and the separated precipitate is washed with deionized water until it becomes neutral. The precipitate is dried at 125 ° C. for 4 hours, and the dried precipitate is fired at 600 ° C. for 4 hours in a muffle furnace.

Here, the preparation of the Ni-Nd-Gd / silica gel coprecipitation catalyst includes the following steps. The saturated sodium silicate solution is adjusted to pH 1.5 with 6 mol / L nitrate, and the molar ratio of Ni: Nd is 1: 0.06 and the molar ratio of Ni: Gd is 1: 0.05. Nickel nitrate and nitrate. Add an aqueous solution of neodymium and gadolinium nitrate. The weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 6% by weight of sodium silicate. Then, the prepared solution is adjusted to pH 9.7 with a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by a centrifugation method, and the separated precipitate is washed with deionized water until it becomes neutral. The precipitate is dried at 125 ° C. for 4 hours, and the dried precipitate is fired at 550 ° C. for 4 hours in a muffle furnace.

Step 2) The pretreated C9 resin is catalytically hydrogenated in a fixed floor.

The C9 resin is dissolved with cyclohexane at a solubility of 15 wt% and the solution is passed through a filtration column of white clay to adsorb insoluble gels, asphaltene and small amounts of free heavy metals onto the white clay. Then, the pretreated C9 resin solution is catalytically hydrogenated.

The conditions for catalytic hydrogenation are a reaction temperature of 350 ° C., a reaction pressure of 18 MPa, a volumetric space velocity of 0.6 h ^-1 , and a volume ratio of hydrogen to C9 resin of 600: 1.

As can be seen from FIG. 6, the absorption peak of the carbon-hydrogen bond on the carbon ^- carbon double bond at 3041 cm ^-1 is the absorption of the carbon-hydrogen bond on the carbon-carbon double bond at 3041 cm-1 in FIG. Significantly smaller than the peak. Further, the bromine value of the C9 resin is reduced from 34 gBr / 100 g to 1.3 g Br / 100 g, and the Gardner color number is 0.6. This indicates that the catalyst is effective for catalytic hydrogenation of the C9 resin.

The method for catalytic hydrogenation of C9 resin includes the following steps 1 and 2.

Step 1) Put the Zr-Mo-Y / silica gel co-precipitation catalyst in the first half of the fixed bed, put the Ni-Nd-Gd / silica gel co-precipitation catalyst in the second half of the fixed bed, and put the high purity of 99.9999% in the fixed bed. Hydrogen gas is introduced and reduced at a reduction temperature of 500 ° C. and a reduction time of 8 hours.

Here, the preparation of the Zr-Mo-Y / silica gel coprecipitation catalyst includes the following steps. The saturated sodium silicate solution is adjusted to pH 1 with 6 mol / L nitric acid, and zirconium nitrate, molybdenum nitrate and molybdenum nitrate having a Zr: Mo molar ratio of 1: 0.3 and a Zr: Y molar ratio of 1: 0.09. Add an aqueous solution of yttrium nitrate. The weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution is 6% by weight of sodium silicate. The prepared solution is adjusted to pH 9.5 with a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by a centrifugation method, and the separated precipitate is washed with deionized water until it becomes neutral, and then the precipitate is settled. The product is dried at 125 ° C. for 4 hours, and the dried precipitate is fired at 650 ° C. for 5 hours in a muffle furnace.

Here, the preparation of the Ni-Nd-Gd / silica gel coprecipitation catalyst includes the following steps. The saturated sodium silicate solution is adjusted to pH 2 with 6 mol / L nitrate, and nickel nitrate, neodymium nitrate and Ni: Nd having a molar ratio of 1: 0.08 and Ni: Gd having a molar ratio of 1: 0.06. Add an aqueous solution of gadrinium nitrate. The weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 8% by weight of sodium silicate. The prepared solution is adjusted to pH 10 with a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by centrifugation, the separated precipitate is washed with deionized water until neutral, and then the precipitate is removed. It is dried at 125 ° C. for 4 hours, and the dried precipitate is calcined at 600 ° C. for 4 hours in a muffle furnace.

Step 2) The pretreated C9 resin is catalytically hydrogenated in a fixed floor.

The C9 resin is dissolved with cyclohexane at a solubility of 10 wt%, the solution is passed through a filtration column of white clay, and insoluble gel, asphaltene and a small amount of free heavy metal are adsorbed on the white clay. Then, the pretreated C9 resin solution is catalytically hydrogenated.

The conditions for catalytic hydrogenation are a reaction temperature of 400 ° C., a reaction pressure of 20 MPa, a volumetric space velocity of 0.7 h ^-1 , and a volume ratio of hydrogen to C9 resin of 700: 1.

As can be seen from FIG. 8, the absorption peak of the carbon-hydrogen bond on the carbon ^- carbon double bond at 3041 cm ^-1 is the absorption of the carbon-hydrogen bond on the carbon-carbon double bond at 3041 cm-1 in FIG. Significantly smaller than the peak. Further, the bromine value of the C9 resin is reduced from 34 gBr / 100 g to 0.6 gBr / 100 g, and the Gardner color number is 0.7. This indicates that the catalyst is effective for catalytic hydrogenation of the C9 resin.

The method for catalytic hydrogenation of C9 resin includes the following steps 1 and 2.

Step 1) Put the Zr-Mo-Y / silica gel co-precipitation catalyst in the first half of the fixed bed, put the Ni-Nd-Gd / silica gel co-precipitation catalyst in the second half of the fixed bed, and put the high purity of 99.9999% in the fixed bed. Hydrogen gas is introduced and reduced at a reduction temperature of 450 ° C. and a reduction time of 6 hours.

Here, the preparation of the Zr-Mo-Y / silica gel coprecipitation catalyst includes the following steps. The saturated sodium silicate solution is adjusted to pH 1.5 with 6 mol / L nitric acid, and the molar ratio of Zr: Mo is 1: 0.3 and the molar ratio of Zr: Y is 1: 0.02. Add an aqueous solution of molybdenum and yttrium nitrate. The weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution is 9% by weight of sodium silicate. Then, the prepared solution is adjusted to pH 10 with a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by a centrifugation method, the separated precipitate is washed with deionized water until it becomes neutral, and then the precipitate is settled. The product is dried at 125 ° C. for 4 hours, and the dried precipitate is fired at 600 ° C. for 5 hours in a muffle furnace.

Here, the preparation of the Ni-Nd-Gd / silica gel coprecipitation catalyst includes the following steps. The saturated sodium silicate solution is adjusted to pH 1 with 6 mol / L nitrate, and nickel nitrate, neodymium nitrate and Ni: Nd having a molar ratio of 1: 0.08 and Ni: Gd having a molar ratio of 1: 0.07. Add an aqueous solution of gadolinium nitrate. The weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 6% by weight of sodium silicate. Then, the prepared solution is adjusted to pH 9.5 with a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by a centrifugation method, and the separated precipitate is washed with deionized water until it becomes neutral. The precipitate is dried at 125 ° C. for 4 hours, and the dried precipitate is fired at 550 ° C. for 4 hours in a muffle furnace.

Step 2) The pretreated C9 resin is catalytically hydrogenated in a fixed floor.

The C9 resin is dissolved with ethylcyclohexane at a solubility of 15 wt% and the solution is passed through a filtration column of white clay to adsorb insoluble gels, asphaltene and small amounts of free heavy metals onto the white clay. Then, the C9 resin solution after the pretreatment is subjected to catalytic hydrogenation.

The conditions for catalytic hydrogenation are a reaction temperature of 300 ° C., a reaction pressure of 20 MPa, a volumetric space velocity of 0.8 h ^-1 , and a volume ratio of hydrogen to C9 resin of 700: 1.

As can be seen from FIG. 10, the absorption peak of the carbon-hydrogen bond on the carbon ^- carbon double bond at 3041 cm ^-1 is the absorption of the carbon-hydrogen bond on the carbon-carbon double bond at 3041 cm-1 in FIG. Significantly smaller than the peak. Further, the bromine value of the C9 resin is reduced from 34 gBr / 100 g to 1.5 g Br / 100 g, and the number of Gardner colors is 1.7. This indicates that the catalyst is effective for catalytic hydrogenation of the C9 resin.

Claims (6)

1) Put the Zr-Mo-Y / silica gel coprecipitation catalyst in the first half of the fixed bed, put the Ni-Nd-Gd / silica gel coprecipitation catalyst in the second half of the fixed bed, introduce hydrogen gas and reduce it.
2) The pretreated C9 resin is catalytically hydrogenated in the fixed floor.
A method for catalytic hydrogenation of a C9 resin. To prepare the Zr-Mo-Y / silica gel co-precipitation catalyst, a saturated sodium silicate solution was adjusted to pH 1-2 with 5-7 mol / L nitrate, and the molar ratio of Zr: Mo was 1: 0.1-1. Aqueous solutions of zirconium nitrate, molybdenum nitrate and yttrium nitrate having a molar ratio of: 0.5 and Zr: Y of 1: 0.05 to 1: 0.3 are added to prepare a solution containing zirconium nitrate, molybdenum nitrate and The weight of ittrium nitrate is adjusted to 5 to 10% of the weight of sodium silicate, the prepared solution is adjusted to pH 9 to 10 with a saturated sodium carbonate solution to form a precipitate, and the precipitate is separated by centrifugation and the separated precipitate. The solution is washed with deionized water until neutral, the precipitate is dried at 100-150 ° C for 3-5 hours, and the dried precipitate is baked in a muffle furnace at 500-700 ° C for 3-5 hours. Including the steps to do
To prepare the Ni-Nd-Gd / silica gel co-precipitation catalyst, a saturated sodium silicate solution was adjusted to pH 1 to 2 with 5 to 7 mol / L nitrate, and the molar ratio of Ni: Nd was 1: 0.03 to 1. Nickel nitrate, neodymite and The weight of gadolinium nitrate is 5 to 10% of the weight of sodium silicate, the prepared solution is adjusted to pH 9 to 10 with saturated sodium carbonate solution to form a precipitate, and the precipitate is separated by centrifugation and separated. The solution is washed with deionized water until neutral, the precipitate is dried at 100-150 ° C for 3-5 hours, and the dried precipitate is baked in a muffle furnace at 500-700 ° C for 3-5 hours. Including steps to do,
The method for catalytic hydrogenation of a C9 resin according to claim 1. The hydrogen gas reduction conditions of the Zr-Mo-Y / silica gel coprecipitation catalyst and the Ni-Nd-Gd / silica gel coprecipitation catalyst are such that a high-purity hydrogen gas is introduced, the reduction temperature is 350 to 500 ° C., and the reduction time is 5 to 5. It is to reduce in 10 hours,
The method for catalytic hydrogenation of a C9 resin according to claim 1. The conditions for contact hydrogenation are a reaction temperature of 250 to 450 ° C., a reaction pressure of 10 to 25 MPa, a volumetric space velocity of 0.1 to 1.0 h ^-1 , and a volume ratio of hydrogen to C9 resin of 400: 1 to 900. 1
The method for catalytic hydrogenation of a C9 resin according to claim 1. The condition for the pretreatment of the C9 resin is to dissolve the C9 resin with cyclohexane or ethylcyclohexane at a solubility of 5 to 20 wt% and pass the solution through a filtration column of white clay or diatomaceous earth.
The method for catalytic hydrogenation of a C9 resin according to claim 1. The Zr-Mo-Y / silica gel co-precipitation catalyst and the Ni-Nd-Gd / silica gel co-precipitation catalyst have a surface area of 90 to 150 m ² / g and a pore size of 50 to 100 nm occupying 10 to 20%.
The method for catalytic hydrogenation of a C9 resin according to any one of claims 1 to 5.

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