CN111333752B - Hydrogenation catalysis method of carbon nine resin - Google Patents

Hydrogenation catalysis method of carbon nine resin Download PDF

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CN111333752B
CN111333752B CN202010128078.7A CN202010128078A CN111333752B CN 111333752 B CN111333752 B CN 111333752B CN 202010128078 A CN202010128078 A CN 202010128078A CN 111333752 B CN111333752 B CN 111333752B
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carbon
resin
precipitate
nitrate
silica gel
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CN111333752A (en
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胡敏杰
黄辉
徐卫红
李颖
张皓荐
肖勋文
王斌
房江华
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Ningbo University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B01J35/19—
    • B01J35/613—
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    • B01J35/66—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention relates to a hydrogenation catalysis method of carbon nine resin, which is characterized in that: 1) putting Zr-Mo-Y/silica gel coprecipitation catalyst in the front half section of the fixed bed, putting Ni-Nd-Gd/silica gel coprecipitation catalyst in the rear half section of the fixed bed, and introducing hydrogen for reduction; 2) and hydrogenating and catalyzing the pretreated carbon nine resin in the fixed bed. Different catalysts capable of reacting under the same catalysis condition are placed in the front section and the rear section of the fixed bed, the two different catalysts have different emphasis points in the action, but the two catalysts can play the roles under the same condition and have complementary functions, the synergistic effect of the two catalysts plays a good catalysis effect, the production process is simplified, and the production cost is saved.

Description

Hydrogenation catalysis method of carbon nine resin
Technical Field
The invention relates to hydrogenation catalysis of petroleum resin, in particular to a hydrogenation catalysis method of carbon nine resin.
Background
Carbon nine resins are by-products obtained when ethylene is produced by cracking. The carbon-nine resin is subjected to hydrogenation catalysis to saturate double bonds and partial benzene rings in the resin, remove residual halogen elements in the polymerization process of the resin, improve the chromaticity, the photo-thermal stability, the oxidation stability and the ultraviolet resistance of the resin, improve the product quality and expand the application. With the development of the application of the adhesive and the sealant, particularly, the application of the transparent pressure-sensitive adhesive tape, the outdoor sealant, the disposable sanitary product, the medical adhesive tape, the road sign paint and the polyolefin modifier requires petroleum resin with light color, no odor and good stability, and the carbon nine resin is one of the petroleum resins, so that the market demand for the hydrogenated carbon nine resin is rapidly increased, the hydrogenation catalytic technology development of the carbon nine resin is promoted, and the selection of the catalyst is a key for influencing the quality of the hydrogenated carbon nine resin finished product.
The carbon nine resin raw material components are complex (more color development groups, gel, S, Cl and other impurities are common), the resin hydrogenation catalyst mainly comprises two types of catalysts of noble metal and non-noble metal, the noble metal catalyst mainly comprises palladium catalyst and palladium-platinum catalyst, and the catalyst has the advantages of high activity, low starting temperature, high product yield and good quality, but has the defects of sensitivity to sulfur and other poisons and inactivation. The non-noble metal catalyst is nickel catalyst, nickel-tungsten catalyst or nickel sulfide-molybdenum catalyst loaded on diatomite or alumina-diatomite, and the catalyst has strong sulfur resistance, but the catalyst has the defects of low activity, high bromine number of the product, serious hydrogenation degradation, high resin yield of the product of about 80 percent, softening point reduction from 120 ℃ to 9 ℃ and short service life. Therefore, in the prior art, the carbon nine resin is subjected to segmented hydrogenation catalysis by using different catalysts.
Chinese patent CN102924659A discloses a two-stage fixed bed resin hydrogenation method, wherein the first stage catalyst is Ni/Al2O3Mainly for removing sulfur from the raw resin. The second stage is noble metal Pt-Pd/Al2O3Hydrogenation catalyst, mainly hydrogenation decoloration treatment; the hydrogenation reaction pressure of the first-stage hydrodesulfurization is 2.0-6.0 MPa, the reaction temperature is 250-350 ℃, and the liquid space velocity is 1-5 h-1The hydrogenation reaction pressure of the two-stage hydrogenation decolorization is 6.0-12.0 MPa, the reaction temperature is 250-350 ℃, and the liquid airspeed is 1-5 h-1Fixed bed high pressure catalytic hydrogenation treatment is adopted. The method gives full play to the advantages of the two-stage catalyst and prolongs the service life of the noble metal catalyst. But the disadvantage is that the catalyst activity is still to be improved; with Al2O3As a load carrier, the catalyst is unevenly dispersed on the load carrier, so that the catalytic effect is poor; two-stage catalyst is adoptedThe same pressurizing condition can not be completed in the same fixed bed, the production efficiency is lower, and pressure interference exists in the actual operation process, which affects the quality of the final carbon nine resin.
In summary, the existing carbon nine resin hydrogenation catalyst has the problems of uneven dispersion of the catalyst on the carrier, poor catalytic effect and the like. Therefore, it is required to develop a hydrogenation catalytic method of carbon nine resin with high catalytic efficiency and simple process
Disclosure of Invention
The invention aims to solve the technical problem of providing a hydrogenation catalysis method for preparing carbon nine resin with good chromaticity, low bromine value and simple process aiming at the current situation of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a hydrogenation catalysis method of carbon nine resin is characterized in that: 1) putting Zr-Mo-Y/silica gel coprecipitation catalyst in the front half section of the fixed bed, putting Ni-Nd-Gd/silica gel coprecipitation catalyst in the rear half section of the fixed bed, and introducing hydrogen for reduction; 2) and hydrogenating and catalyzing the pretreated carbon nine resin in the fixed bed.
Preferably, the preparation of the Zr-Mo-Y/silica gel coprecipitation catalyst comprises the following steps: adjusting the pH value of the saturated solution of sodium silicate to 1-2 by using 5-7 mol/L nitric acid, pouring an aqueous solution of zirconium nitrate, molybdenum nitrate and yttrium nitrate, and adding Zr: the Mo molar ratio is 1: 0.1-1: 0.5, Zr: the molar ratio of Y is 1: 0.05-1: 0.3, regulating the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution to be 5-10% of the weight of sodium silicate, regulating the pH value of the prepared solution to be 9-10 by using a saturated sodium carbonate solution to form a precipitate, separating the precipitate by using a centrifugal method, washing the separated precipitate to be neutral by using deionized water, drying the precipitate for 3-5 hours at the temperature of 100-150 ℃, and roasting the dried precipitate for 3-5 hours at the temperature of 500-700 ℃ in a muffle furnace;
the preparation method of the Ni-Nd-Gd/silica gel coprecipitation catalyst comprises the following steps: adjusting the pH value of the saturated solution of sodium silicate to 1-2 by using 5-7 mol/L nitric acid, pouring nickel nitrate, neodymium nitrate and gadolinium nitrate aqueous solution, and adding Ni: the molar ratio of Nd is 1: 0.03 to 1: 0.1, Ni: gd molar ratio is 1: 0.01-1: 0.08, the weight of the nickel nitrate, the neodymium nitrate and the gadolinium nitrate in the prepared solution is 5-10% of that of the sodium silicate, the prepared solution is adjusted to a pH value of 9-10 by using a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by using a centrifugal method, the separated precipitate is washed to be neutral by using deionized water, the precipitate is dried for 3-5 hours at 100-150 ℃, and the dried precipitate is roasted for 3-5 hours at 500-700 ℃ in a muffle furnace.
Preferably, the hydrogen reduction conditions of the Zr-Mo-Y/silica gel and Ni-Nd-Gd/silica gel coprecipitation catalyst are as follows: introducing high-purity hydrogen gas for reduction at the temperature of 350-500 ℃ for 5-10 hours.
Preferably, the hydrogenation catalytic conditions are as follows: the reaction temperature is 250-450 ℃, the reaction pressure is 10-25 MPa, and the volume space velocity is 0.1-1.0 h-1The volume ratio of hydrogen to carbon nine resin is 400: 1-900: 1.
preferably, the pretreatment conditions of the carbon nine resin are as follows: dissolving the carbon nine resin with cyclohexane or ethyl cyclohexane in the solubility of 5-20 wt%, and filtering the solution with white clay or diatomite filtering column.
Preferably, the surface area of the Zr-Mo-Y/silica gel and Ni-Nd-Gd/silica gel coprecipitation catalyst is 90-150 square meters per gram, and the pore diameter of 50-100 nm accounts for 10-20%.
Compared with the prior art, the invention has the advantages that: 1) different catalysts capable of reacting under the same catalysis condition are placed at the front section and the rear section of the fixed bed, the Zr-Mo-Y/silica gel catalyst can remove most of sulfur and halogen in the carbon nine resin and also has a certain bromine removal effect, the Ni-Nd-Gd/silica gel catalyst mainly has the deep hydrogenation function and further has the function of removing other hetero atoms, residual sulfur and nitrogen in the carbon nine resin can be continuously removed, the two different catalysts have different side points for playing roles, but the two catalysts can play the roles under the same condition and have complementary functions, the synergistic effect of the two catalysts plays a good role in catalysis, the production process is simplified, and the production cost is saved.
2) The Zr-Mo-Y/silica gel and the Ni-Nd-Gd/silica gel catalyst are prepared by a precipitation method, so that the metal catalyst is uniformly dispersed on the surface of the silica gel, the surface area of the coprecipitation catalyst is 90-150 square meters per gram, the pore diameter of 50-100 nm accounts for 10-20%, the uniformly dispersed metal catalyst is fully contacted with the carbon-nine resin, the dosage of the catalyst is reduced, and the catalytic efficiency is improved.
3) The synergistic effect of the Zr-Mo-Y/silica gel and the Ni-Nd-Gd/silica gel catalyst can reduce the bromine number in the carbon nine resin from 32.5g Br/100g to below 6.0g Br/100g, and the Gardner color is controlled to below 6.0, which indicates that the catalyst is effective for hydrogenation catalysis of the carbon nine resin.
Drawings
FIG. 1 is an infrared spectrum of a carbon nine resin of example 1 before hydrogenation catalysis.
FIG. 2 is an infrared spectrum of a carbon nine resin of example 1 of the present invention after hydrogenation catalysis.
FIG. 3 is an infrared spectrum of a carbon nine resin of example 2 before hydrogenation catalysis.
FIG. 4 is an infrared spectrum of a carbon nine resin of example 2 of the present invention after hydrogenation catalysis.
FIG. 5 is an infrared spectrum of a carbon nine resin of example 3 before hydrogenation catalysis.
FIG. 6 is an infrared spectrum of a carbon nine resin of example 3 after hydrogenation catalysis.
FIG. 7 is an infrared spectrum of a carbon nine resin of example 4 before hydrogenation catalysis.
FIG. 8 is an infrared spectrum of a carbon nine resin of example 4 of the present invention after hydrogenation catalysis.
FIG. 9 is an infrared spectrum of a carbon nine resin of example 5 before hydrogenation catalysis.
FIG. 10 is an infrared spectrum of a carbon nine resin of example 5 after hydrogenation catalysis.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples.
Example 1
The hydrogenation catalysis method of the carbon nine resin comprises the following steps: 1) putting Zr-Mo-Y/silica gel coprecipitation catalyst in the front half section of the fixed bed, putting Ni-Nd-Gd/silica gel coprecipitation catalyst in the rear half section of the fixed bed, and introducing 99.999% high-purity hydrogen gas into the fixed bed for reduction at the reduction temperature of 350 ℃ for 10 hours.
The preparation method of the Zr-Mo-Y/silica gel coprecipitation catalyst comprises the following steps: regulating the pH value of the saturated solution of sodium silicate to 1 by using 6mol/L nitric acid, and pouring aqueous solutions of zirconium nitrate, molybdenum nitrate and yttrium nitrate, wherein Zr: the Mo molar ratio is 1: 0.1, Zr: the molar ratio of Y is 1: 0.3, regulating the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution to 5% of the weight of sodium silicate, regulating the prepared solution to a pH value of 9 by using a saturated sodium carbonate solution to form a precipitate, separating the precipitate by using a centrifugal method, washing the separated precipitate to be neutral by using deionized water, drying the precipitate for 4 hours at 125 ℃, and roasting the dried precipitate for 3 hours at 500 ℃ in a muffle furnace;
the preparation method of the Ni-Nd-Gd/silica gel coprecipitation catalyst comprises the following steps: regulating the pH value of the saturated solution of sodium silicate to 2 by using 6mol/L nitric acid, and pouring nickel nitrate, neodymium nitrate and gadolinium nitrate aqueous solution, wherein the weight ratio of Ni: the molar ratio of Nd is 1: 0.1, Ni: gd molar ratio is 1: 0.01, the weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 10% of the weight of sodium silicate, the prepared solution is adjusted to the pH value of 10 by using a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by using a centrifugal method, the separated precipitate is washed to be neutral by using deionized water, the precipitate is dried for 4 hours at 125 ℃, and the dried precipitate is roasted for 5 hours at 700 ℃ in a muffle furnace.
2) And (3) hydrogenating and catalyzing the pretreated carbon nine resin in a fixed bed.
The carbon nine resin was dissolved with cyclohexane at a solubility of 5 wt%, and the solution was passed through a clay filter column. Making insoluble gel, asphaltene and a small amount of free heavy metal be adsorbed on clay, and making the pretreated carbon nine resin solution be fed into catalytic hydrogenation process.
The hydrogenation catalysis conditions are as follows: the reaction temperature is 450 ℃, the reaction pressure is 10MPa, and the volume space velocity is 0.1h-1The volume ratio of hydrogen to carbon nine resin is 400: 1.
3041cm can be seen from FIG. 2-1The absorption peak of hydrocarbon at the carbon-carbon double bond is significantly smaller than 30 in FIG. 141cm-1The carbon-carbon double bond hydrogen absorption peak, the bromine number of the carbon-nine resin is reduced from 34g Br/100g to 3.2g Br/100g, and the Gardner color is 3.2, which shows that the catalyst is effective for the hydrogenation catalysis of the carbon-nine resin.
Example 2
The hydrogenation catalysis method of the carbon nine resin comprises the following steps: 1) putting Zr-Mo-Y/silica gel coprecipitation catalyst in the front half section of the fixed bed, putting Ni-Nd-Gd/silica gel coprecipitation catalyst in the rear half section of the fixed bed, and introducing 99.999% high-purity hydrogen gas into the fixed bed for reduction at the reduction temperature of 500 ℃ for 5 hours.
The preparation method of the Zr-Mo-Y/silica gel coprecipitation catalyst comprises the following steps: regulating the pH value of the saturated solution of sodium silicate to 2 by using 6mol/L nitric acid, and pouring aqueous solutions of zirconium nitrate, molybdenum nitrate and yttrium nitrate, wherein Zr: the Mo molar ratio is 1: 0.5, Zr: the molar ratio of Y is 1: 0.05, regulating the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution to 10% of the weight of sodium silicate, adjusting the pH value of the prepared solution to 10 by using a saturated sodium carbonate solution to form a precipitate, separating the precipitate by using a centrifugal method, washing the separated precipitate to be neutral by using deionized water, drying the precipitate for 4 hours at 125 ℃, and roasting the dried precipitate for 5 hours at 700 ℃ in a muffle furnace;
the preparation method of the Ni-Nd-Gd/silica gel coprecipitation catalyst comprises the following steps: regulating the pH value of the saturated solution of sodium silicate to 1 by using 6mol/L nitric acid, and pouring nickel nitrate, neodymium nitrate and gadolinium nitrate aqueous solution, wherein the weight ratio of Ni: the molar ratio of Nd is 1: 0.03, Ni: gd molar ratio is 1: 0.08, the weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 5 percent of that of sodium silicate, the prepared solution is adjusted to a pH value of 9 by using a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by using a centrifugal method, the separated precipitate is washed to be neutral by using deionized water, the precipitate is dried for 4 hours at 125 ℃, and the dried precipitate is roasted for 3 hours at 500 ℃ in a muffle furnace.
2) And (3) hydrogenating and catalyzing the pretreated carbon nine resin in a fixed bed.
The carbon nine resin was dissolved with ethyl cyclohexane at a solubility of 20 wt%, and the solution was passed through a clay filter column. Making insoluble gel, asphaltene and a small amount of free heavy metal be adsorbed on clay, and making the pretreated carbon nine resin solution be fed into catalytic hydrogenation process.
The hydrogenation catalysis conditions are as follows: the reaction temperature is 250 ℃, the reaction pressure is 25MPa, and the volume space velocity is 1.0h-1The volume ratio of hydrogen to carbon nine resin is 900: 1.
3041cm can be seen from FIG. 4-1The absorption peak of carbon-carbon double bond is obviously less than 3041cm in figure 3-1The carbon-carbon double bond hydrogen absorption peak, the bromine number of the carbon-nine resin is reduced from 34g Br/100g to 5.3g Br/100g, and the Gardner color is 5.9, which shows that the catalyst is effective for the hydrogenation catalysis of the carbon-nine resin.
Example 3
The hydrogenation catalysis method of the carbon nine resin comprises the following steps: 1) putting Zr-Mo-Y/silica gel coprecipitation catalyst in the front half section of the fixed bed, putting Ni-Nd-Gd/silica gel coprecipitation catalyst in the rear half section of the fixed bed, and introducing 99.999% high-purity hydrogen gas into the fixed bed for reduction at the reduction temperature of 400 ℃ for 7 hours.
The preparation method of the Zr-Mo-Y/silica gel coprecipitation catalyst comprises the following steps: adjusting the pH value of the saturated solution of sodium silicate to 1.5 by using 6mol/L nitric acid, pouring aqueous solutions of zirconium nitrate, molybdenum nitrate and yttrium nitrate, wherein the ratio of Zr: the Mo molar ratio is 1: 0.2, Zr: the molar ratio of Y is 1: 0.1, regulating the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution to be 7% of the weight of sodium silicate, regulating the pH value of the prepared solution to be 9.5 by using a saturated sodium carbonate solution to form a precipitate, separating the precipitate by using a centrifugal method, washing the separated precipitate to be neutral by using deionized water, drying the precipitate for 4 hours at 125 ℃, and roasting the dried precipitate for 4 hours at 600 ℃ in a muffle furnace;
the preparation method of the Ni-Nd-Gd/silica gel coprecipitation catalyst comprises the following steps: regulating the pH value of the saturated solution of sodium silicate to 1.5 by using 6mol/L nitric acid, pouring nickel nitrate, neodymium nitrate and gadolinium nitrate aqueous solution, Ni: the molar ratio of Nd is 1: 0.06, Ni: gd molar ratio is 1: 0.05, the weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 6% of the weight of sodium silicate, the prepared solution is adjusted to the pH value of 9.7 by using a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by using a centrifugal method, the separated precipitate is washed to be neutral by using deionized water, the precipitate is dried for 4 hours at 125 ℃, and the dried precipitate is roasted for 4 hours at 550 ℃ in a muffle furnace.
2) And (3) hydrogenating and catalyzing the pretreated carbon nine resin in a fixed bed.
The carbon nine resin was dissolved with cyclohexane at a solubility of 15 wt%, and the solution was passed through a clay filter column. Making insoluble gel, asphaltene and a small amount of free heavy metal be adsorbed on clay, and making the pretreated carbon nine resin solution be fed into catalytic hydrogenation process.
The hydrogenation catalysis conditions are as follows: the reaction temperature is 350 ℃, the reaction pressure is 18MPa, and the volume space velocity is 0.6h-1The volume ratio of hydrogen to carbon nine resin is 600: 1.
3041cm can be seen from FIG. 6-1The absorption peak of carbon-carbon double bond is obviously less than 3041cm in figure 5-1The carbon-carbon double bond hydrogen absorption peak, the bromine number of the carbon-nine resin is reduced from 34g Br/100g to 1.3g Br/100g, and the Gardner color is 0.6, which shows that the catalyst is effective for the hydrogenation catalysis of the carbon-nine resin.
Example 4
The hydrogenation catalysis method of the carbon nine resin comprises the following steps: 1) putting Zr-Mo-Y/silica gel coprecipitation catalyst in the front half section of the fixed bed, putting Ni-Nd-Gd/silica gel coprecipitation catalyst in the rear half section of the fixed bed, and introducing 99.999% high-purity hydrogen gas into the fixed bed for reduction at the reduction temperature of 500 ℃ for 8 hours.
The preparation method of the Zr-Mo-Y/silica gel coprecipitation catalyst comprises the following steps: regulating the pH value of the saturated solution of sodium silicate to 1 by using 6mol/L nitric acid, and pouring aqueous solutions of zirconium nitrate, molybdenum nitrate and yttrium nitrate, wherein Zr: the Mo molar ratio is 1: 0.3, Zr: the molar ratio of Y is 1: 0.09, regulating the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution to be 6% of the weight of sodium silicate, regulating the pH value of the prepared solution to be 9.5 by using a saturated sodium carbonate solution to form a precipitate, separating the precipitate by using a centrifugal method, washing the separated precipitate to be neutral by using deionized water, drying the precipitate for 4 hours at 125 ℃, and roasting the dried precipitate for 5 hours at 650 ℃ in a muffle furnace;
the preparation method of the Ni-Nd-Gd/silica gel coprecipitation catalyst comprises the following steps: regulating the pH value of the saturated solution of sodium silicate to 2 by using 6mol/L nitric acid, and pouring nickel nitrate, neodymium nitrate and gadolinium nitrate aqueous solution, wherein the weight ratio of Ni: the molar ratio of Nd is 1: 0.08, Ni: gd molar ratio is 1: 0.06, the weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 8% of the weight of sodium silicate, the prepared solution is adjusted to a pH value of 10 by using a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by using a centrifugal method, the separated precipitate is washed to be neutral by using deionized water, the precipitate is dried for 4 hours at 125 ℃, and the dried precipitate is roasted for 4 hours at 600 ℃ in a muffle furnace.
2) And (3) hydrogenating and catalyzing the pretreated carbon nine resin in a fixed bed.
The carbon nine resin was dissolved with cyclohexane at a solubility of 10 wt%, and the solution was passed through a clay filter column. Making insoluble gel, asphaltene and a small amount of free heavy metal be adsorbed on clay, and making the pretreated carbon nine resin solution be fed into catalytic hydrogenation process.
The hydrogenation catalysis conditions are as follows: the reaction temperature is 400 ℃, the reaction pressure is 20MPa, and the volume space velocity is 0.7h-1The volume ratio of hydrogen to carbon nine resin is 700: 1.
3041cm can be seen from FIG. 8-1The absorption peak of carbon-carbon double bond is obviously less than 3041cm in figure 7-1The carbon-carbon double bond hydrogen absorption peak, the bromine number of the carbon-nine resin is reduced from 34g Br/100g to 0.6g Br/100g, and the Gardner color is 0.7, which shows that the catalyst is effective for the hydrogenation catalysis of the carbon-nine resin.
Example 5
The hydrogenation catalysis method of the carbon nine resin comprises the following steps: 1) putting Zr-Mo-Y/silica gel coprecipitation catalyst in the front half section of the fixed bed, putting Ni-Nd-Gd/silica gel coprecipitation catalyst in the rear half section of the fixed bed, and introducing 99.999% high-purity hydrogen gas into the fixed bed for reduction at the reduction temperature of 450 ℃ for 6 hours.
The preparation method of the Zr-Mo-Y/silica gel coprecipitation catalyst comprises the following steps: adjusting the pH value of the saturated solution of sodium silicate to 1.5 by using 6mol/L nitric acid, pouring aqueous solutions of zirconium nitrate, molybdenum nitrate and yttrium nitrate, wherein the ratio of Zr: the Mo molar ratio is 1: 0.3, Zr: the molar ratio of Y is 1: 0.02, regulating the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution to 9% of the weight of sodium silicate, adjusting the pH value of the prepared solution to 10 by using a saturated sodium carbonate solution to form a precipitate, separating the precipitate by using a centrifugal method, washing the separated precipitate to be neutral by using deionized water, drying the precipitate for 4 hours at 125 ℃, and roasting the dried precipitate for 5 hours at 600 ℃ in a muffle furnace;
the preparation method of the Ni-Nd-Gd/silica gel coprecipitation catalyst comprises the following steps: regulating the pH value of the saturated solution of sodium silicate to 1 by using 6mol/L nitric acid, and pouring nickel nitrate, neodymium nitrate and gadolinium nitrate aqueous solution, wherein the weight ratio of Ni: the molar ratio of Nd is 1: 0.08, Ni: gd molar ratio is 1: 0.07, the weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 6% of the weight of sodium silicate, the prepared solution is adjusted to the pH value of 9.5 by using a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by using a centrifugal method, the separated precipitate is washed to be neutral by using deionized water, the precipitate is dried for 4 hours at 125 ℃, and the dried precipitate is roasted for 4 hours at 550 ℃ in a muffle furnace.
2) And (3) hydrogenating and catalyzing the pretreated carbon nine resin in a fixed bed.
The carbon nine resin was dissolved with ethyl cyclohexane at a solubility of 15 wt%, and the solution was passed through a clay filter column. Making insoluble gel, asphaltene and a small amount of free heavy metal be adsorbed on clay, and making the pretreated carbon nine resin solution be fed into catalytic hydrogenation process.
The hydrogenation catalysis conditions are as follows: the reaction temperature is 300 ℃, the reaction pressure is 20MPa, and the volume space velocity is 0.8h-1The volume ratio of hydrogen to carbon nine resin is 700: 1.
3041cm can be seen from FIG. 10-1The absorption peak of carbon-carbon double bond is obviously less than 3041cm in FIG. 9-1The carbon-carbon double bond hydrogen absorption peak, the bromine number of the carbon-nine resin is reduced from 34g Br/100g to 1.5g Br/100g, and the Gardner color is 1.7, which shows that the catalyst is effective for the hydrogenation catalysis of the carbon-nine resin.

Claims (5)

1. A hydrogenation catalysis method of carbon nine resin is characterized in that: 1) putting Zr-Mo-Y/silica gel coprecipitation catalyst in the front half section of the fixed bed, putting Ni-Nd-Gd/silica gel coprecipitation catalyst in the rear half section of the fixed bed, and introducing hydrogen for reduction; 2) hydrogenating and catalyzing the pretreated carbon nine resin in the fixed bed;
the preparation method of the Zr-Mo-Y/silica gel coprecipitation catalyst comprises the following steps: adjusting the pH value of the saturated solution of sodium silicate to 1-2 by using 5-7 mol/L nitric acid, pouring an aqueous solution of zirconium nitrate, molybdenum nitrate and yttrium nitrate, and adding Zr: the Mo molar ratio is 1: 0.1-1: 0.5, Zr: the molar ratio of Y is 1: 0.05-1: 0.3, regulating the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution to be 5-10% of the weight of sodium silicate, regulating the pH value of the prepared solution to be 9-10 by using a saturated sodium carbonate solution to form a precipitate, separating the precipitate by using a centrifugal method, washing the separated precipitate to be neutral by using deionized water, drying the precipitate for 3-5 hours at the temperature of 100-150 ℃, and roasting the dried precipitate for 3-5 hours at the temperature of 500-700 ℃ in a muffle furnace;
the preparation method of the Ni-Nd-Gd/silica gel coprecipitation catalyst comprises the following steps: adjusting the pH value of the saturated solution of sodium silicate to 1-2 by using 5-7 mol/L nitric acid, pouring nickel nitrate, neodymium nitrate and gadolinium nitrate aqueous solution, and adding Ni: the molar ratio of Nd is 1: 0.03 to 1: 0.1, Ni: gd molar ratio is 1: 0.01-1: 0.08, the weight of the nickel nitrate, the neodymium nitrate and the gadolinium nitrate in the prepared solution is 5-10% of that of the sodium silicate, the prepared solution is adjusted to a pH value of 9-10 by using a saturated sodium carbonate solution to form a precipitate, the precipitate is separated by using a centrifugal method, the separated precipitate is washed to be neutral by using deionized water, the precipitate is dried for 3-5 hours at 100-150 ℃, and the dried precipitate is roasted for 3-5 hours at 500-700 ℃ in a muffle furnace.
2. The method for hydrocatalyzing a carbon nine resin as recited in claim 1, wherein: the hydrogen reduction conditions of the Zr-Mo-Y/silica gel and Ni-Nd-Gd/silica gel coprecipitation catalyst are as follows: introducing high-purity hydrogen gas for reduction at the temperature of 350-500 ℃ for 5-10 hours.
3. Carbon nine of claim 1The hydrogenation catalysis method of the resin is characterized in that: the hydrogenation catalysis conditions are as follows: the reaction temperature is 250-450 ℃, the reaction pressure is 10-25 MPa, and the volume space velocity is 0.1-1.0 h-1The volume ratio of hydrogen to carbon nine resin is 400: 1-900: 1.
4. the method for hydrocatalyzing a carbon nine resin as recited in claim 1, wherein: the pretreatment conditions of the carbon nine resin are as follows: dissolving the carbon nine resin with cyclohexane or ethyl cyclohexane in the solubility of 5-20 wt%, and filtering the solution with white clay or diatomite filtering column.
5. The process for the hydrocatalysis of a carbon nine resin according to any one of claims 1 to 4 wherein: the surface area of the Zr-Mo-Y/silica gel and Ni-Nd-Gd/silica gel coprecipitation catalyst is 90-150 square meters per gram, and the pore diameter of 50-100 nm accounts for 10-20%.
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