CN109759056B - Preparation method of hydrogenation catalyst for C5/C9 copolymerized petroleum resin and hydrogenation method - Google Patents
Preparation method of hydrogenation catalyst for C5/C9 copolymerized petroleum resin and hydrogenation method Download PDFInfo
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Abstract
The invention discloses a preparation method and a hydrogenation method of a hydrogenation catalyst for C5/C9 copolymerized petroleum resin, wherein three mixtures of pseudo-boehmite, alumina and kieselguhr or four mixtures of pseudo-boehmite, aluminum hydroxide, alumina and kieselguhr are used as raw powder, a nitric acid solution is prepared, and phosphoric acid accounting for 0.5-5% of the total amount of the raw powder is added into the nitric acid solution; gelling, kneading, forming, drying, roasting, crushing to obtain oxygen-containing aluminum carrier particles, carrying out hydrothermal treatment under a high-temperature condition, soaking the treated aluminum carrier particles in an alkali metal or alkaline earth metal aqueous solution, drying, loading a noble metal active component, and roasting at 380-450 ℃ to obtain a loaded bi-component noble metal catalyst; the hydrogenation process adopts a fixed bed hydrogenation process, and the solution after hydrogenation removes free sulfur and chlorine generated by reaction, and the light-colored and colorless hydrogenated petroleum resin is obtained by removing the solvent and oligomer.
Description
Technical Field
The invention relates to a preparation method of a hydrogenation catalyst for C5/C9 copolymerized petroleum resin and a hydrogenation method, the catalyst and the hydrogenation method are suitable for the hydrogenation process of the C5/C9 copolymerized petroleum resin, the catalyst is a modified active alumina carrier loaded bi-component noble metal catalyst, the hydrogenation process adopts a fixed bed hydrogenation process, a raw material solution is metered, pressurized and mixed with high-pressure hydrogen and then enters a reactor, hydrogenation reaction is carried out on a hydrogenation catalyst bed layer, the content of unsaturated double bonds in the petroleum resin is reduced, residual sulfur, chlorine and chromogenic groups of the resin in the polymerization process are removed, and free sulfur, chlorine generated by the reaction are removed from the solution after hydrogenation to obtain light-colored and colorless hydrogenated petroleum resin through removing a solvent and oligomers. The catalyst is chlorine-resistant and sulfur-resistant, and the process has no special requirements on the content of impurities such as sulfur, halogen and the like in the reaction raw material petroleum resin, and does not need to carry out dechlorination and desulfurization pretreatment on the raw material petroleum resin.
Background
The petroleum resin is a solid or viscous liquid polymer with relatively low molecular weight prepared by polymerization of by-products C5 and C9 fractions of an ethylene device serving as main raw materials, has the characteristics of low acid value, good miscibility, low melting point, good adhesiveness, water resistance, chemical resistance and the like, and is widely applied to the fields of road marking paint, printing ink, rubber processing, adhesives and the like at present. The C5/C9 copolymerized petroleum resin is produced by C5 fraction and C9 fraction in a certain proportion, has the advantages of light color of C5 petroleum resin and high softening point of C9 petroleum resin, and is widely applied to rubber processing, adhesives and paints. The C5/C9 copolymerized petroleum resin is gradually substituted for the expensive C5 petroleum resin in the fields of hot melt adhesives, rubber and tires, and is accepted by wide customers at home and abroad. In the field of rubber and tyre, the copolymerized petroleum resin is added, so that not only can the adhesive force between rubber particles be increased, but also the adhesive force between the rubber particles and the cord can be improved. In the fields of hot melt adhesives, adhesives and bonding agents, the C5/C9 copolymerized petroleum resin not only can provide better initial viscosity, but also can be used for adjusting the durability and bonding strength of the viscosity of a mixture of the adhesive and the resin like rosin resin.
The hue and the stability of the petroleum resin are important indexes which need to be considered when the petroleum resin is applied, the hydrogenation technology of the petroleum resin is an important way for improving the hue and the stability of the petroleum resin, the resin can be changed into white or transparent after being hydrogenated, the stability is enhanced, in addition, the adhesion, the weather resistance and the compatibility with EVA can be improved, the quality of the resin is improved, and the application field is greatly widened.
The C5/C9 copolymerized petroleum resin has the advantages of both C5 petroleum resin and C9 petroleum resin, but has high requirements on hydrogenation catalyst and hydrogenation process due to the characteristics of molecular structure and polymerization process. The C5/C9 copolymerized petroleum resin has larger molecular weight, contains a large amount of unsaturated double bonds, particularly aromatic hydrocarbon petroleum resin with benzene rings, is in a chain and ring structure, polymer molecules extend on the surface of the catalyst to form high steric hindrance, and simultaneously, the polymer molecules are easy to deposit on the surface of the catalyst to cover a surface active center, so that the activity of the catalyst is reduced, in order to improve the activity of the catalyst, the reaction temperature is required to be increased, and as a result, the polymerization coking process is accelerated, so that the catalyst is inactivated more quickly. The existing petroleum resin polymerization production technology does not generally control the content of harmful substances (such as gel, sulfur, chlorine, some heavy metals and the like) causing poisoning of a resin hydrogenation catalyst, a C5/C9 copolymerized petroleum resin polymerization process generally adopts a catalytic polymerization process, although a resin product is subjected to post-treatment processes such as alkali washing neutralization and water washing, the content of residual chlorine in the resin is still 500-5000 ppm, the residual chlorine can cause poisoning and inactivation of the hydrogenation catalyst, and hydrogen chloride can be generated in the hydrogenation process to severely corrode equipment, so that the hydrogenation of the petroleum resin requires low content of impurities such as halogen, sulfur and the like in raw materials, or the raw material petroleum resin is subjected to dechlorination and desulfurization pretreatment. Therefore, the hydrogenation process of the C5/C9 copolymerized petroleum resin belongs to the processes of high temperature, high pressure and high corrosion, the operation conditions are harsh, and the hydrogenation catalyst is required to have the characteristics of high activity and high deactivation resistance.
The polymerization process of the C5/C9 copolymer resin reported at present is mainly cationic polymerization, and due to the C5 and C9 fractions, a certain content of chlorine and sulfur exists in a resin product, so that the residual sulfur and chlorine in the resin are removed in addition to double bonds and colored groups in the hydrogenation process of the copolymer resin, which is also the work focus in the research of hydrogenation of the C5/C9 copolymer petroleum resin. In the current patents and reports for the hydrogenation process of the C5/C9 copolymer resin, the hydrogenation process comprises a batch kettle type hydrogenation process and a fixed bed continuous hydrogenation process, and hydrogenation catalysts comprise a nickel catalyst and a noble metal catalyst. Patent CN1962706 discloses a hydrogenation process of C5/C9 copolymerized petroleum resin, which adopts a fixed bed for continuous hydrogenation, the catalyst is a supported nickel catalyst, and bromine number and thermal stability of the petroleum resin after hydrogenation are improved. Patent CN1803871 discloses a method for hydrogenating and decoloring petroleum resin C5 and C9 under the catalysis of modified skeleton nickel, which improves the saturation of products and has water white color. Patent CN101538350 discloses an industrial preparation process and equipment for hydrogenating C5/C9 petroleum resin, wherein the process adopts a slurry kettle type hydrogenation process, a catalyst is used for modifying a skeletal nickel catalyst, and the process adopts special reaction equipment. However, the nickel catalyst is not sensitive to impurities such as sulfur and chlorine, the degradation of resin in the reaction process is the disadvantage of the catalyst, the noble metal catalyst has high hydrogenation activity but is sensitive to impurities, and the catalyst is easily inactivated due to the existence of sulfur and chlorine, so that the requirement on the hydrogenated resin raw material is high, or the petroleum resin raw material is subjected to desulfurization and dechlorination pretreatment before the hydrogenation step, so that the hydrogenation process becomes complicated.
Disclosure of Invention
In order to solve the problems of the prior art, the invention provides a hydrogenation catalyst for C5/C9 copolymerized petroleum resin and a preparation method thereof, the catalyst is suitable for the hydrogenation process of the C5/C9 copolymerized petroleum resin, the hydrogenation catalyst is a supported catalyst, a catalyst carrier is active alumina, pore enlargement, hydrothermal treatment and alkaline earth metal modification are carried out on the carrier in the preparation process of the carrier, and a supported active component on the carrier is a bi-component precious metal.
The specific technical scheme is as follows:
a catalyst for hydrogenation of C5/C9 copolymerized petroleum resin is a supported catalyst, the catalyst carrier is active alumina, and the active component loaded on the carrier is bi-component noble metal; the noble metal is two of VIII group element, rare earth element, Ib group element or IIb element.
The noble metal loaded on the hydrogenation catalyst carrier is preferably two of Pt, Pd, Ru, Rh or Ni; wherein the Pt loading is 0.2-1%, the Pd loading is 0.2-1.2%, the Ru loading is 0.2-1%, the Rh loading is 0.1-1%, and the Ni loading is 0.2-1.5%.
The preparation method of the catalyst for hydrogenation of the C5/C9 copolymerized petroleum resin comprises the steps of mixing three kinds of pseudo-boehmite, alumina and kieselguhr or four kinds of pseudo-boehmite, aluminum hydroxide, alumina and kieselguhr to serve as raw powder, preparing a nitric acid solution, wherein the mass concentration of the nitric acid solution is 3-5%, the using amount of the nitric acid solution is 50-65% of the total mass of the raw powder, and 0.5-5% of phosphoric acid of the total mass of the raw powder is added into the nitric acid solution; the method comprises the steps of gelatinizing raw powder by using a nitric acid mixed solution added with phosphoric acid, kneading, forming, drying, roasting at 450-600 ℃, crushing to obtain oxygen-containing aluminum carrier particles, carrying out hydrothermal treatment for 2-5 hours at the high temperature of 300-500 ℃, soaking the treated aluminum carrier particles in an alkali metal or alkaline earth metal aqueous solution, drying, loading a noble metal active component, and roasting at 380-450 ℃ to obtain the noble metal-loaded catalyst.
The hydrogenation catalyst carrier raw powder is three mixtures of pseudo-boehmite, alumina and diatomite or four mixtures of pseudo-boehmite, aluminum hydroxide, alumina and diatomite, and the mass percentage is as follows:
the aluminum hydroxide is nano-scale aluminum hydroxide with the average particle size of 10-30 nm.
The preferred hydrothermal treatment temperature is 350-450 ℃, and the treatment time is 3-4 hours.
The alkali metal or alkaline earth metal is an alkali metal carbonate and an alkaline earth metal nitrate solution.
The method for hydrogenating the C5/C9 copolymerized petroleum resin by using the catalyst comprises the steps of loading the catalyst into a constant-temperature section of a reactor, reducing and activating the catalyst in hydrogen, boosting the pressure of the reactor to 3-10 MPa after reduction is finished, simultaneously raising the temperature to 200-300 ℃, and enabling a C5/C9 copolymerized petroleum resin raw material solution with the concentration of 10-30% to pass through a metering pump at a liquid volume airspeed of 1-4 h -1 Pumping the mixture into a fixed bed hydrogenation reactor, feeding the mixture and hydrogen into a preheating section of the reactor together, fully mixing and preheating the mixture to reach a reaction temperature, feeding the mixture into a hydrogenation catalyst bed layer for hydrogenation reaction, feeding a gas-liquid mixed product after the reaction into a desulfurization and dechlorination tank for removing sulfur and chlorine generated by the reaction, and then carrying out gas-liquid separation after passing through a condenser; and removing byproducts such as solvent, oligomer and the like from the separated liquid mixed product to obtain a solid resin product.
Preferably, the hydrogenation reaction temperature is 200-260 ℃, the pressure is 7-9 MPa, and the space velocity of the liquid of the inner treatment capacity in unit time of the hydrogenation catalyst is 1-3 h -1 The hydrogen-oil ratio is 200-400, and the feeding concentration of the C5/C9 copolymerized petroleum resin solution is 10-20%.
The concrete description is as follows:
the carrier raw powder is prepared by mixing three of pseudo-boehmite, alumina and kieselguhr or four of pseudo-boehmite, alumina and kieselguhr, the carrier prepared by adopting the pseudo-boehmite, the alumina and the kieselguhr has larger pore volume, pore diameter and specific surface area, the commercially available nano-scale aluminum hydroxide with the average particle size of 10-30 nm is used in the invention, the addition amount of the nano-scale aluminum hydroxide is 0-40%, the use amount of nitric acid can be reduced in the gluing process after the nano-scale aluminum hydroxide is added, the acidity of the catalyst can be reduced, the occurrence of petroleum resin degradation reaction in the hydrogenation reaction process is reduced, the reduction of the softening point of a product caused by the degradation reaction is avoided, and the specific surface agent of the carrier is seriously reduced due to the excessively large addition amount.
Phosphoric acid is added into the nitric acid solution in the gelling process to increase the pore volume and the pore diameter of the carrier and play a role of a pore-expanding agent, but the mechanical strength of the carrier is seriously reduced due to the excessive use amount of the phosphoric acid, so that the use amount of the phosphoric acid is 0.5-5% of the total amount of the raw powder.
The prepared carrier is modified by alkali metal to reduce the acidity of the surface of the carrier, so that the occurrence of petroleum resin degradation reaction in the hydrogenation reaction process is reduced, when carrier particles are impregnated by the alkali metal or alkaline earth metal aqueous solution, 100ml of the alkali metal or alkaline earth metal aqueous solution is prepared, 100ml of the molded, crushed and sieved alumina carrier particles are taken, the carrier is impregnated in the alkali metal or alkaline earth metal solution, the carrier is dried at the temperature of 60-80 ℃, and then dried at the temperature of 110-130 ℃ for 3-8 hours, and the alkali solution is preferably alkali carbonate and alkaline earth metal nitrate solution.
The active component of the catalyst adopts bi-component noble metal, so that the sintering resistance and impurity resistance of the noble metal element microcrystal can be improved, and the longer hydrogenation service life is provided. The noble metal loaded on the catalyst carrier is two of VIII group elements, Ib group elements and IIb elements.
The method comprises the steps of preparing 200ml of mixed aqueous solution containing two noble metals of Pt, Pd, Ru, Rh and Ni by loading the noble metals of Pt, Pd, Ru, Rh and Ni on a hydrogenation catalyst carrier, averagely dividing the aqueous solution into four equal parts of 50ml, taking 50ml of prepared active alumina carrier particles, soaking the carrier in 50ml of the mixed solution of the noble metals, drying at the temperature of 60-80 ℃, drying at the temperature of 110-130 ℃ for 3-10 hours, repeating the operation for 4 times, and completely soaking the 200ml of mixed bimetallic aqueous solution. And heating to 380-450 ℃ and roasting for 4 hours to obtain the noble metal-loaded catalyst.
The invention prepares the C5/C9 copolymerized petroleum resin air-entrapping catalyst, selects the raw materials and the dosage for preparing the catalyst carrier, and obtains large pore volume, pore diameter and specific surface area by adding phosphoric acid into nitric acid solution in the gelling process and carrying out hydrothermal treatment on the carrier, so that the catalyst has higher hydrogenation activity. The method of adding nano-level aluminum hydroxide into the raw powder to reduce the amount of nitric acid and modifying the catalyst carrier by alkaline earth metal is adopted to reduce the surface acidity of the catalyst, thereby reducing the occurrence of petroleum resin degradation reaction in the hydrogenation reaction process and preventing the softening point and the molecular weight of the petroleum resin from being reduced. The active component of the catalyst adopts bi-component noble metal, so that the sintering resistance and impurity resistance of the noble metal element microcrystal can be improved, and the longer hydrogenation service life is provided.
The experimental device adopts a single-tube fixed bed hydrogenation device, the catalyst reduction adopts a dry method in-device reduction mode, the catalyst prepared by the method is filled into a constant-temperature section of a reactor to be subjected to reduction activation for 3-8 hours at 240-300 ℃ in hydrogen, a bed layer of the reactor is cooled to be below 100 ℃ after the catalyst reduction is finished, and a hydrogenation device system is pressurized to be prepared to be 7-9 MPa, so that a petroleum resin hydrogenation experiment can be carried out.
The raw material petroleum resin for hydrogenation is C5/C9 copolymerized petroleum resin.
Suitable solvents for preparing the raw material petroleum resin solution comprise saturated alkane, saturated polyalkyl cycloalkane, aromatic hydrocarbon solvents and the like, such as cyclohexane, heptane, octane, methylcyclohexane, hydrogenated aromatic raffinate oil and the like.
The C5/C9 copolymerized petroleum resin raw material is subjected to hydrogenation reaction in a hydrogenation catalyst bed layer, so that the content of unsaturated double bonds in the petroleum resin is reduced, and the bromine number of the product is reduced; residual sulfur, chlorine and chromogenic groups in the polymerization process on resin molecules are removed through hydrogenation reaction, free sulfur and chlorine generated in a reaction product solution are removed, the Gardner chroma of the product resin is improved, and the sulfur and chlorine content of the product is reduced; the light-colored and colorless hydrogenated petroleum resin is obtained after the solvent and the oligomer are removed, the catalyst is a chlorine-resistant and sulfur-resistant catalyst, the process has no special requirements on the content of impurities such as sulfur, halogen and the like in the reaction raw material petroleum resin, and the raw material petroleum resin does not need to be subjected to dechlorination and desulfurization pretreatment.
The specific implementation mode is as follows:
example 1
1) Preparing a hydrogenation catalyst:
fully mixing 500g of pseudo-boehmite, 300g of alumina, 200g of diatomite and 100g of nano aluminum hydroxide, weighing 660g of dilute nitric acid aqueous solution with the concentration of 4%, adding 11g of phosphoric acid into the nitric acid solution, fully and uniformly mixing, gelatinizing, kneading, aging for 30 minutes, extruding and molding on a strip extruding machine, drying at 120 ℃, roasting at 125 ℃ for 2 hours, and heating to 520 ℃ for roasting for 4 hours; and crushing and sieving to obtain 10-20 mesh particles.
The catalyst carrier after roasting and crushing is loaded into a fixed bed reactor at a volume space velocity of 3H -1 Deionized water is introduced, and the alumina carrier is subjected to hydrothermal treatment for 2 hours at 500 ℃.
100ml of 0.5 percent magnesium nitrate aqueous solution is prepared, 100ml of sieved alumina carrier particles are taken, the carrier is soaked in alkali metal or alkaline earth metal solution, dried at 60 ℃ and dried for 5 hours at 120 ℃.
Preparing 200ml of noble metal mixed solution containing Pd and Rh, averagely dividing the aqueous solution into four equal parts of 50ml, taking 50ml of prepared activated alumina carrier particles, soaking the carrier in 50ml of mixed bimetallic aqueous solution, drying at 70 ℃, drying for 5 hours at 120 ℃, repeating the operation for 4 times, completing the complete soaking of the 200ml mixed bimetallic aqueous solution, roasting at 120 ℃ for 2 hours, heating to 420 ℃ and roasting for 4 hours to obtain the noble metal catalyst loaded with 0.8 percent Pd and 0.3 percent Rh.
2) The catalyst prepared in the above step is used for hydrogenation experiments, and the hydrogenation experiment steps are as follows:
dissolving C5/C9 copolymerized petroleum resin in methylcyclohexane to prepare a raw material solution with the content of C5/C9 copolymerized petroleum resin being 10%.
15ml of the prepared C5/C9 copolymerized petroleum resin hydrogenation catalyst is loaded into a fixed bed reactor, reduction activation is carried out in hydrogen at 300 ℃ for 6 hours, then the temperature is reduced to be below 100 ℃, the pressure of a fixed bed hydrogenation device is increased to 8MPa, and simultaneously the temperature of the reactor is increased to 220 ℃. The C5/C9 copolymerized petroleum resin raw material solution is fed by a metering pump at a liquid volume space velocity of 2h -1 Pumping into a fixed bed hydrogenation reactor, entering a preheating section of the reactor together with fresh hydrogen, fully mixing and preheating to reach a reaction temperature, entering a hydrogenation reaction catalyst bed layer, and carrying out hydrogenation reaction, wherein the hydrogen-oil ratio is 300. The gas-liquid mixed product enters a desulfurization and dechlorination tank to remove sulfur and chlorine generated by the reaction, and then enters a high-pressure gas-liquid separation tank after being condensed to carry out gas-liquid separation; the gas is discharged after being measured by a soap bubble flowmeter through a back pressure valve; and discharging the liquid mixed product from the bottom of the high-pressure gas-liquid separation tank, and removing byproducts such as solvent, oligomer and the like from the liquid mixed product by using a falling film evaporator to obtain a solid resin product. Hydrogenated liquid petroleumThe resin solution is used for measuring bromine number, Gardner color, sulfur content and chlorine content, and the solid product after solvent removal is used for measuring softening point. The experimental conditions of example 1 are shown in table 1.
TABLE 1 Experimental data for desulfurization and dechlorination effects of hydroprocessing process
Example 2
1) Preparing a hydrogenation catalyst:
fully mixing 500g of pseudo-boehmite, 300g of alumina, 200g of diatomite and 20g of nano aluminum hydroxide, weighing 500g of dilute nitric acid aqueous solution with the concentration of 4%, adding 5g of phosphoric acid into the nitric acid solution, fully and uniformly mixing, gelatinizing, kneading, aging for 30 minutes, extruding and molding on a strip extruding machine, drying, heating to 450 ℃, roasting for 4 hours, crushing and sieving, and taking 10-20-mesh particles.
Loading the roasted and crushed catalyst carrier into a fixed bed reactor at a volume space velocity of 3H -1 Deionized water is introduced, and the alumina carrier is subjected to hydrothermal treatment for 2 hours at 500 ℃.
Preparing 200ml of mixed bimetallic aqueous solution from Pd and Ru chlorides, evenly dividing the aqueous solution into four equal parts of 50ml, taking 50ml of hydrothermal activated alumina carrier particles, soaking the carrier in 50ml of mixed bimetallic aqueous solution, drying for 6 hours, repeating the operation for 4 times, and then completing the complete soaking of the 200ml mixed bimetallic aqueous solution. Heating to 380 ℃ and roasting for 4 hours to obtain the noble metal catalyst loaded with 0.4 percent of Ru and 0.6 percent of Pd.
2) The catalyst prepared in the above step is used for hydrogenation experiments, and the hydrogenation experiment steps are as follows:
dissolving C5/C9 copolymerized petroleum resin in methylcyclohexane to prepare a raw material solution with the content of C5/C9 copolymerized petroleum resin being 10%.
15ml of the prepared catalyst is loaded into a fixed bed reactor, reduction activation is carried out for 4 hours at 280 ℃ in hydrogen, then the temperature is reduced to 100 ℃, a fixed bed hydrogenation device is pressurized to be prepared to be 8MPa, and simultaneously the reactor is heated to 230 ℃.
The C5/C9 copolymerized petroleum resin raw material solution with the concentration of 10 percent is fed into a metering pump at the liquid volume space velocity of 2h -1 Pumping into a fixed bed hydrogenation reactor, entering a preheating section of the reactor together with fresh hydrogen, fully mixing and preheating to reach a reaction temperature, and entering a hydrogenation catalyst bed layer for hydrogenation reaction. The reaction conditions are that the temperature is 230 ℃, the pressure is 8MPa, and the volume space velocity of the feeding liquid of the raw material solution is 2h -1 Hydrogen volume space velocity of 400h -1 The hydrogen-oil ratio was 200. The gas-liquid mixed product enters a desulfurization and dechlorination tank to remove sulfur and chlorine generated by the reaction, and then enters a high-pressure gas-liquid separation tank after being condensed to carry out gas-liquid separation; the gas is discharged after being measured by a soap bubble flowmeter through a back pressure valve; and discharging the liquid mixed product from the bottom of the high-pressure gas-liquid separation tank, and removing byproducts such as solvent, oligomer and the like from the liquid mixed product by using a falling film evaporator to obtain a solid resin product.
The bromine number of the hydrogenated liquid petroleum resin solution is 1.19gBr/100g Gardner color of 0.5, and the softening point of the solid product after solvent removal is 113 ℃.
Example 3
1) Preparing a hydrogenation catalyst:
fully mixing 300g of pseudo-boehmite, 300g of alumina and 400g of diatomite, weighing 650g of dilute nitric acid aqueous solution with the concentration of 5%, gelatinizing, kneading, aging for 30 minutes, performing extrusion molding on a strip extruding machine, drying, and heating to 450 ℃ for roasting for 4 hours; and crushing and sieving to obtain 10-20 mesh particles.
Loading the roasted and crushed catalyst carrier into a fixed bed reactor at a volume space velocity of 3H -1 Deionized water is introduced, and the alumina carrier is subjected to hydrothermal treatment for 3 hours at the temperature of 450 ℃.
Preparing 200ml of mixed bimetallic aqueous solution from Pt and Pd chlorides, evenly dividing the aqueous solution into four equal parts of 50ml, taking 50ml of the prepared active alumina carrier particles, soaking the carrier in 50ml of mixed bimetallic aqueous solution, drying for 6 hours, repeating the operation for 4 times, completing the complete soaking of the 200ml of mixed bimetallic aqueous solution, heating to 450 ℃, and roasting for 4 hours to obtain the noble metal catalyst with the load of 0.2 percent Pd and 1 percent Pt.
2) The catalyst prepared in the above step is used for hydrogenation experiments, and the hydrogenation experiment steps are as follows:
the C5/C9 copolymerized petroleum resin is dissolved in octane to prepare a raw material solution with the C5/C9 copolymerized petroleum resin content of 10%.
15ml of the prepared catalyst is loaded into a fixed bed reactor, reduction activation is carried out for 4 hours at 280 ℃ in hydrogen, then the temperature is reduced to 100 ℃, a fixed bed hydrogenation device is pressurized to be prepared to be 8MPa, and simultaneously the reactor is heated to 230 ℃.
The C5/C9 copolymerized petroleum resin raw material solution with the concentration of 10 percent is fed into a metering pump at the liquid volume space velocity of 2h -1 Pumping into a fixed bed hydrogenation reactor, entering a preheating section of the reactor together with fresh hydrogen, fully mixing and preheating to reach a reaction temperature, and entering a hydrogenation catalyst bed layer for hydrogenation reaction. The reaction conditions are that the temperature is 230 ℃, the pressure is 8MPa, and the volume space velocity of the feeding liquid of the raw material solution is 2h -1 Hydrogen volume space velocity of 400h -1 The hydrogen-oil ratio was 200. The gas-liquid mixed product enters a desulfurization and dechlorination tank to remove sulfur and chlorine generated by the reaction, and then enters a high-pressure gas-liquid separation tank after being condensed to carry out gas-liquid separation; the gas is discharged after being measured by a soap bubble flowmeter through a back pressure valve; and discharging the liquid mixed product from the bottom of the high-pressure gas-liquid separation tank, and removing byproducts such as solvent, oligomer and the like from the liquid mixed product by using a falling film evaporator to obtain a solid resin product.
The bromine number of the hydrogenated liquid petroleum resin solution is 1.41gBr/100g Gardner color of 0.7, and the softening point of the solid product after solvent removal is 113 ℃.
Example 4
1) Preparing a hydrogenation catalyst:
fully mixing 500g of pseudo-boehmite, 100g of alumina and 400g of diatomite, weighing 600g of dilute nitric acid aqueous solution with the concentration of 5%, gelatinizing, kneading, aging for 30 minutes, performing extrusion molding on a strip extruding machine, drying, and heating to 500 ℃ for roasting for 4 hours; and crushing and sieving to obtain 10-20 mesh particles.
50ml of 0.6% sodium carbonate aqueous solution was prepared, 50ml of the sieved alumina carrier particles were taken, and the carrier was immersed in the solution and dried at 120 ℃ for 5 hours.
Preparing 200ml of mixed bimetallic aqueous solution from Rh and Ru chlorides, averagely dividing the aqueous solution into four equal parts of 50ml, taking 50ml of the prepared active alumina carrier particles, soaking the carrier in 50ml of mixed bimetallic aqueous solution, drying for 6 hours, repeating the operation for 4 times, and then completely soaking the 200ml of mixed bimetallic aqueous solution. Heating to 400 ℃, and roasting for 4 hours to obtain the noble metal catalyst loaded with 0.3 percent of Rh and 1 percent of Ru.
2) The catalyst prepared in the above step is used for hydrogenation experiments, and the hydrogenation experiment steps are as follows:
dissolving the C5/C9 copolymerized petroleum resin in 120# solvent oil to prepare a raw material solution with the content of C5/C9 copolymerized petroleum resin being 10%.
15ml of the prepared catalyst is loaded into a fixed bed reactor, reduction activation is carried out for 4 hours at 280 ℃ in hydrogen, then the temperature is reduced to 100 ℃, a fixed bed hydrogenation device is pressurized to be prepared to be 8MPa, and simultaneously the reactor is heated to 230 ℃.
The C5/C9 copolymerized petroleum resin raw material solution with the concentration of 10 percent is fed into a metering pump at the liquid volume space velocity of 2h -1 Pumping into a fixed bed hydrogenation reactor, entering a preheating section of the reactor together with fresh hydrogen, fully mixing and preheating to reach a reaction temperature, and entering a hydrogenation catalyst bed layer for hydrogenation reaction. The reaction conditions are that the temperature is 230 ℃, the pressure is 8MPa, and the volume space velocity of the feeding liquid of the raw material solution is 2h -1 Hydrogen volume space velocity of 400h -1 The hydrogen-oil ratio was 200. The gas-liquid mixed product enters a desulfurization and dechlorination tank to remove sulfur and chlorine generated by the reaction, and then enters a high-pressure gas-liquid separation tank after being condensed to carry out gas-liquid separation; the gas is discharged after being measured by a soap bubble flowmeter through a back pressure valve; and discharging the liquid mixed product from the bottom of the high-pressure gas-liquid separation tank, and removing byproducts such as solvent, oligomer and the like from the liquid mixed product by using a falling film evaporator to obtain a solid resin product.
The bromine number of the hydrogenated liquid petroleum resin solution is 0.54g Br/100g Gardner color number and 0.4, and the softening point of the solid product after solvent removal is 116 ℃.
Example 5
1) Preparing a hydrogenation catalyst:
fully mixing 400g of pseudo-boehmite, 500g of alumina, 100g of diatomite and 400g of nano aluminum hydroxide, weighing 770g of dilute nitric acid aqueous solution with the concentration of 3%, adding 14g of phosphoric acid into the nitric acid solution, fully and uniformly mixing, gelatinizing, kneading, aging for 30 minutes, performing extrusion molding on a strip extrusion machine, drying, and heating to 450 ℃ for roasting for 4 hours; and crushing and sieving to obtain 10-20 mesh particles.
Loading the roasted and crushed catalyst carrier into a fixed bed reactor at a volume space velocity of 3H -1 Deionized water is introduced, and the alumina carrier is subjected to hydrothermal treatment for 5 hours at the temperature of 400 ℃.
50ml of a 1% strontium nitrate aqueous solution was prepared, 50ml of hydrothermally treated alumina carrier particles were taken, and the carrier was immersed in the solution and dried for 5 hours.
Preparing 200ml of mixed bimetallic aqueous solution from Pd and Ni chlorides, evenly dividing the aqueous solution into four equal parts of 50ml, taking 50ml of the prepared active alumina carrier particles, soaking the carrier in 50ml of mixed bimetallic aqueous solution, drying for 6 hours, repeating the operation for 4 times, completing the complete soaking of the 200ml mixed bimetallic aqueous solution, heating to 420 ℃, and roasting for 4 hours to obtain the noble metal catalyst with the load of 0.9 percent Pd and 0.2 percent Ni.
2) The hydrogenation experiment was carried out using the catalyst prepared in the above procedure, which was the same as in example 2:
the bromine number of the hydrogenated liquid petroleum resin solution is 1.47g Br/100g Gardner color number and is 0.9, and the softening point of the solid product after solvent removal is 117 ℃.
Example 6
1) Preparing a hydrogenation catalyst:
fully mixing 700g of pseudo-boehmite, 250g of alumina and 50g of diatomite, weighing 650g of dilute nitric acid aqueous solution with the concentration of 5%, adding 10g of phosphoric acid into the nitric acid solution, fully and uniformly mixing, gelatinizing, kneading, aging for 30 minutes, performing extrusion molding on a strip extruding machine, drying, and heating to 500 ℃ for roasting for 4 hours; and crushing and sieving to obtain 10-20 mesh particles.
Calcining the crushed catalystThe carrier is loaded into a fixed bed reactor at a volumetric space velocity of 3H -1 Deionized water is introduced, and the alumina carrier is subjected to hydrothermal treatment for 3 hours at the temperature of 300 ℃.
50ml of 0.2% potassium carbonate aqueous solution was prepared, 50ml of the hydrothermally treated alumina carrier particles were taken, and the carrier was immersed in the solution and dried for 5 hours.
Preparing 200ml of mixed bimetallic aqueous solution from Ru and Pd chlorides, averagely dividing the aqueous solution into four equal parts of 50ml, taking 50ml of the prepared active alumina carrier particles, soaking the carrier in 50ml of mixed bimetallic aqueous solution, drying for 6 hours, repeating the operation for 4 times, completing the complete soaking of the 200ml of mixed bimetallic aqueous solution, heating to 430 ℃, and roasting for 4 hours to obtain the noble metal catalyst with the load of 0.5 percent Pt and 0.5 percent Ni.
2) The hydrogenation experiment was carried out using the catalyst prepared in the above procedure, which was the same as in example 2:
the bromine number of the hydrogenated liquid petroleum resin solution is 0.78gBr/100g Gardner color number and 0.7, and the softening point of the solid product after solvent removal is 115 ℃.
Example 7
1) Preparing a hydrogenation catalyst:
fully mixing 550g of pseudo-boehmite, 250g of alumina, 200gg of diatomite and 100g of nano aluminum hydroxide, weighing 660g of dilute nitric acid aqueous solution with the concentration of 4%, gelatinizing, kneading, aging for 30 minutes, performing extrusion molding on a strip extruder, drying, and heating to 550 ℃ for roasting for 4 hours; and crushing and sieving to obtain 10-20 mesh particles.
Loading the roasted and crushed catalyst carrier into a fixed bed reactor at a volume space velocity of 3H -1 Deionized water is introduced, and the alumina carrier is subjected to hydrothermal treatment for 4 hours at the temperature of 350 ℃.
50ml of a 0.5% magnesium nitrate aqueous solution was prepared, 50ml of the hydrothermally treated alumina carrier particles were taken, the carrier was immersed in the solution, and dried for 5 hours.
Preparing 200ml of mixed bimetallic aqueous solution by Pd and Rh chlorides, averagely dividing the aqueous solution into four equal parts of 50ml, taking 50ml of the prepared active alumina carrier particles, soaking the carrier in 50ml of mixed bimetallic aqueous solution, drying for 6 hours, repeating the above operations for 4 times, completing the complete soaking of the 200ml of mixed bimetallic aqueous solution, heating to 400 ℃, and roasting for 4 hours to obtain the noble metal catalyst with the load of 1.2m percent Pd and 0.1 percent Rh.
2) The hydrogenation experiment was carried out using the catalyst prepared in the above procedure, which was the same as in example 2:
the bromine number of the hydrogenated liquid petroleum resin solution is 0.24g Br/100g Gardner color number and 0.2, and the softening point of the solid product after solvent removal is 119 ℃.
Example 8
1) Preparing a hydrogenation catalyst:
fully mixing 600g of pseudo-boehmite, 300g of alumina, 100g of diatomite and 80g of nano aluminum hydroxide, weighing 550g of dilute nitric acid aqueous solution with the concentration of 5%, adding 50g of phosphoric acid into the nitric acid solution, fully and uniformly mixing, gelatinizing, kneading, aging for 30 minutes, performing extrusion molding on a strip extruder, drying, and heating to 600 ℃ for roasting for 4 hours; and crushing and sieving to obtain 10-20 mesh particles.
50ml of 0.3% aqueous calcium nitrate solution was prepared, 50ml of the crushed and sieved carrier particles were taken, and the carrier was immersed in the solution and dried for 5 hours.
Preparing mixed bimetallic aqueous solution of 200ml from Ni and Ru chlorides, averagely dividing the aqueous solution into four equal parts of 50ml, taking 50ml of the prepared active alumina carrier particles, soaking the carrier in the mixed bimetallic aqueous solution of 50ml, drying for 6 hours, repeating the operation for 4 times, completing the complete soaking of the mixed bimetallic aqueous solution of 200ml, heating to 430 ℃, and roasting for 4 hours to obtain the noble metal catalyst with the load of 1.5 percent of Ni and 0.2 percent of Ru.
2) The hydrogenation experiment was carried out using the catalyst prepared in the above procedure, which was the same as in example 2:
the bromine number of the hydrogenated liquid petroleum resin solution is 0.84gBr/100g Gardner color number and 0.4, and the softening point of the solid product after solvent removal is 116 ℃.
Example 9
1) Preparing a hydrogenation catalyst:
fully mixing 500g of pseudo-boehmite, 300g of alumina, 200g of diatomite and 50g of nano aluminum hydroxide, weighing 500g of dilute nitric acid aqueous solution with the concentration of 5%, gelatinizing, kneading, aging for 30 minutes, performing extrusion molding on a strip extruder, drying, and heating to 530 ℃ for roasting for 4 hours; and crushing and sieving to obtain 10-20 mesh particles.
Preparing 200ml of mixed bimetallic aqueous solution from Rh and Pt chlorides, averagely dividing the aqueous solution into four equal parts of 50ml, taking 50ml of prepared active alumina carrier particles, soaking the carrier in 50ml of mixed bimetallic aqueous solution, drying for 6 hours, repeating the operation for 4 times, completing the complete soaking of the 200ml of mixed bimetallic aqueous solution, heating to 430 ℃ and roasting for 4 hours to obtain the noble metal catalyst with the load of 1% Rh and 0.2% Pt. A hydrogenation evaluation test was conducted in the same manner as in example 2.
The bromine number of the hydrogenated liquid petroleum resin solution is 1.37gBr/100g, the Gardner color is 0.3, and the softening point of the solid product after solvent removal is 115 ℃.
TABLE 2 preparation of hydrogenation catalyst and hydrogenation Effect
Examples 10 to 17
Fully mixing 500g of pseudo-boehmite, 300g of alumina, 200g of diatomite and 60g of nano aluminum hydroxide, weighing 550g of 5% dilute nitric acid aqueous solution, adding 15g of phosphoric acid into the nitric acid solution, fully and uniformly mixing, gelatinizing, kneading, aging for 30 minutes, extruding and molding on a strip extruding machine, drying at 120 ℃, roasting at 125 ℃ for 2 hours, and heating to 500 ℃ for roasting for 4 hours; crushing and sieving, taking 10-20 mesh particles, preparing 100ml of 0.5% magnesium nitrate aqueous solution, taking 100ml of sieved alumina carrier particles, soaking the carrier in an alkali metal or alkaline earth metal solution, drying at 60 ℃, and drying for 5 hours at 120 ℃; preparing 200ml of noble metal mixed solution containing Pd and Rh, averagely dividing the aqueous solution into four equal parts of 50ml, taking 50ml of prepared active alumina carrier particles, soaking the carrier in 50ml of mixed bimetallic aqueous solution, drying at 70 ℃, drying for 5 hours at 120 ℃, repeating the operation for 4 times, completing the complete soaking of the 200ml mixed bimetallic aqueous solution, roasting at 120 ℃ for 2 hours, heating to 450 ℃ and roasting for 4 hours to obtain the noble metal catalyst loaded with 1 percent of Pd and 0.2 percent of Rh.
Dissolving C5/C9 copolymerized petroleum resin in methylcyclohexane to prepare a raw material solution with the content of C5/C9 copolymerized petroleum resin being 10-20%.
15ml of the prepared C5/C9 copolymerized petroleum resin hydrogenation catalyst is loaded into a fixed bed reactor, reduction activation is carried out in hydrogen at 240-300 ℃ for 3-8 hours, then the temperature is reduced to be below 100 ℃, a fixed bed hydrogenation device is pressurized to be prepared to be 7-9 MPa, and simultaneously the reactor is heated to be 200-300 ℃. The C5/C9 copolymerized petroleum resin raw material solution is fed into a metering pump at a liquid volume space velocity of 1-4 h -1 Pumping into a fixed bed hydrogenation reactor, entering a preheating section of the reactor together with fresh hydrogen, fully mixing and preheating to reach a reaction temperature, entering a hydrogenation reaction catalyst bed layer, and carrying out hydrogenation reaction, wherein the hydrogen-oil ratio is 100-400. The gas-liquid mixed product enters a desulfurization and dechlorination tank to remove sulfur and chlorine generated by the reaction, and then enters a high-pressure gas-liquid separation tank after being condensed to carry out gas-liquid separation; the gas is discharged after being measured by a soap bubble flowmeter through a back pressure valve; and discharging the liquid mixed product from the bottom of the high-pressure gas-liquid separation tank, and removing byproducts such as solvent, oligomer and the like from the liquid mixed product by using a falling film evaporator to obtain a solid resin product. The bromine number and the Gardner color are measured by the liquid petroleum resin solution after hydrogenation, and the softening point is measured by the solid product after solvent removal. The experimental conditions for examples 10 to 17 are shown in Table 3.
TABLE 3 Experimental data for hydrogenation process conditions
The method for preparing the hydrogenation catalyst and the hydrogenation method for the C5/C9 copolymerized petroleum resin disclosed and proposed by the invention can be realized by those skilled in the art by referring to the contents in the text, appropriately changing the condition route and the like, and although the method and the preparation technology of the invention have been described by the preferred embodiments, the related technical personnel can obviously modify or recombine the method and the technical route described herein to realize the final preparation technology without departing from the contents, the spirit and the scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (11)
1. A catalyst for hydrogenating C5/C9 copolymerized petroleum resin is characterized in that a hydrogenation catalyst is a supported catalyst, a catalyst carrier is active alumina, and an active component loaded on the carrier is a bi-component noble metal; the noble metal is two of Pt, Pd, Ru, Rh or Ni; wherein the Pt loading amount is 0.2-1%, the Pd loading amount is 0.2-1.2%, the Ru loading amount is 0.2-1%, the Rh loading amount is 0.1-1%, and the Ni loading amount is 0.2-1.5%;
the preparation method of the catalyst carrier comprises the following steps: mixing three kinds of pseudo-boehmite, alumina and kieselguhr or four kinds of pseudo-boehmite, aluminum hydroxide, alumina and kieselguhr to obtain raw powder, preparing a nitric acid solution, wherein the mass concentration of the nitric acid solution is 3-5%, the dosage of the nitric acid solution is 50-65% of the total mass of the raw powder, and adding phosphoric acid accounting for 0.5-5% of the total mass of the raw powder into the nitric acid solution; the raw powder is gelatinized, kneaded, molded and dried by using a nitric acid mixed solution added with phosphoric acid, roasted at 450-600 ℃, and then crushed to obtain alumina carrier particles, hydrothermal treatment is carried out for 2-5 hours at the high temperature of 300-500 ℃, the treated alumina carrier particles are immersed in an alkali metal or alkaline earth metal aqueous solution, and the catalyst carrier is obtained after drying.
2. The catalyst of claim 1, wherein the hydrogenation catalyst carrier raw powder is three mixtures of pseudo-boehmite, alumina and diatomite or four mixtures of pseudo-boehmite, aluminum hydroxide, alumina and diatomite, and the mass percentage contents are as follows:
30 to 70 percent of pseudo-boehmite,
10 to 50 percent of alumina,
5 to 40 percent of diatomite,
0-40% of aluminum hydroxide.
3. The catalyst according to claim 1 or 2, wherein the aluminum hydroxide is a nano-sized aluminum hydroxide having an average particle diameter of 10 to 30 nm.
4. The catalyst according to claim 1 or 2, wherein the hydrothermal treatment temperature is 350 to 450 ℃ and the treatment time is 3 to 4 hours.
5. Catalyst according to claim 1 or 2, characterized in that the alkali metal or alkaline earth metal is an alkali metal carbonate and an alkaline earth metal nitrate solution.
6. The method for preparing the catalyst for hydrogenation of the C5/C9 copolymerized petroleum resin as claimed in any one of claims 1 to 5, wherein three kinds of pseudo-boehmite, alumina and diatomite or four kinds of pseudo-boehmite, alumina and diatomite are mixed to form raw powder, a nitric acid solution is prepared, wherein the mass concentration of the nitric acid solution is 3-5%, the amount of the nitric acid solution is 50-65% of the total mass of the raw powder, and phosphoric acid accounting for 0.5-5% of the total mass of the raw powder is added into the nitric acid solution; the method comprises the steps of gelatinizing raw powder by using a nitric acid mixed solution added with phosphoric acid, kneading, forming, drying, roasting at 450-600 ℃, crushing to obtain alumina carrier particles, carrying out hydrothermal treatment for 2-5 hours at the high temperature of 300-500 ℃, soaking the treated alumina carrier particles in an alkali metal or alkaline earth metal aqueous solution, drying, loading a noble metal active component, and roasting at 380-450 ℃ to obtain the noble metal-loaded catalyst.
7. The method as set forth in claim 6, characterized in that the hydrogenation catalyst carrier raw powder is three mixtures of pseudo-boehmite, alumina and diatomite or four mixtures of pseudo-boehmite, aluminum hydroxide, alumina and diatomite, and the mass percentages are as follows: 30-70% of pseudo-boehmite, 10-50% of alumina, 5-40% of diatomite and 0-40% of aluminum hydroxide;
the aluminum hydroxide is nano-scale aluminum hydroxide with the average particle size of 10-30 nm.
8. The method according to claim 6, wherein the hydrothermal treatment temperature is 350 to 450 ℃ and the treatment time is 3 to 4 hours.
9. The method as set forth in claim 6, wherein the alkali metal or alkaline earth metal is an alkali metal carbonate and an alkaline earth metal nitrate solution.
10. The method for hydrogenating the C5/C9 copolymerized petroleum resin by using the catalyst as claimed in any one of claims 1 to 5 is characterized in that the catalyst is filled into a constant-temperature section of a reactor to be reduced and activated in hydrogen, after the reduction is finished, the pressure of the reactor is increased to 3-10 MPa, the temperature is increased to 200-300 ℃, and a C5/C9 copolymerized petroleum resin raw material solution with the concentration of 10-30% is pumped by a metering pump at a liquid volume space velocity of 1-4 h -1 Pumping the mixture into a fixed bed hydrogenation reactor, feeding the mixture and hydrogen into a preheating section of the reactor together, fully mixing and preheating the mixture to reach a reaction temperature, feeding the mixture into a hydrogenation catalyst bed layer for hydrogenation reaction, feeding a gas-liquid mixed product after the reaction into a desulfurization and dechlorination tank for removing sulfur and chlorine generated by the reaction, and then feeding the product into a condenser for gas-liquid separation; and removing the solvent and the oligomer from the separated liquid mixed product to obtain a solid resin product.
11. The method of claim 10, wherein the hydrogenation reaction temperature is 200-260 ℃, the pressure is 7-9 MPa, and the liquid space velocity of the inner treatment capacity per unit time of the hydrogenation catalyst is 1-3 h -1 The hydrogen-oil ratio is 200-400, and the feeding concentration of the C5/C9 copolymerized petroleum resin solution is 10-20%.
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