CN112191245A - Ultrathin eggshell type noble metal alloy catalyst for catalytic hydrogenation reaction of C5 petroleum resin and preparation method and application thereof - Google Patents

Ultrathin eggshell type noble metal alloy catalyst for catalytic hydrogenation reaction of C5 petroleum resin and preparation method and application thereof Download PDF

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CN112191245A
CN112191245A CN202011039259.9A CN202011039259A CN112191245A CN 112191245 A CN112191245 A CN 112191245A CN 202011039259 A CN202011039259 A CN 202011039259A CN 112191245 A CN112191245 A CN 112191245A
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reaction
catalyst
petroleum resin
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noble metal
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王建国
杨骏
邓声威
钟兴
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Zhejiang University of Technology ZJUT
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    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B01J35/397—
    • 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
    • B01J37/0201—Impregnation
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
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    • 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

Abstract

The invention discloses an ultrathin eggshell type noble metal alloy catalyst for catalytic hydrogenation reaction of C5 petroleum resin, a preparation method and application thereof, relating to the technical field of catalyst preparation and comprising the following specific steps: 1) firstly, preparing a precursor aqueous solution for later use; 2) putting the precursor aqueous solution prepared in the step 1) into a beaker, and adding Al2O3The materials are stirred and mixed to be uniform and are placed at room temperatureAdsorption; 3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and placing the obtained solid product in a muffle furnace for high-temperature calcination; 4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, roasting in the atmosphere of reducing gas, and after the roasting is finished, obtaining a solid product, namely the catalyst to be prepared2O3The catalyst is applied to the hydrogenation reaction of the C5 resin, and shows excellent catalytic activity and service life.

Description

Ultrathin eggshell type noble metal alloy catalyst for catalytic hydrogenation reaction of C5 petroleum resin and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to an ultrathin eggshell type noble metal alloy catalyst for catalytic hydrogenation reaction of C5 petroleum resin, and a preparation method and application thereof.
Background
The catalytic hydrogenation technology has long been used for the hydrogenation upgrading of petrochemical industry and biomass, so as to obtain better chemical products. The petroleum resin is a byproduct in the petrochemical production process, has simple synthesis process, low production cost, good hydrophobicity and corrosion resistance, and good compatibility with numerous organic matters, and thus, is widely applied in industry. However, petroleum resins also have some disadvantages, such as high brittleness, easy deformation, heavy color, etc., thus limiting their application in some fields. At present, the properties of petroleum resin are improved by some technical means, so that some defects can be overcome, and the application range of the petroleum resin is expanded. As the molecular weight of the C5 petroleum resin is larger than that of other liquid phase hydrogenation reaction materials, the C5 petroleum resin molecule forms high steric hindrance when the surface of the catalyst is stretched, the hydrogenation difficulty is quite large, the required reaction conditions are harsh, and the hydrogenation reaction can be completed under the conditions that the pressure is 9-20MPa and the temperature is 250-300 ℃ by generally requiring the catalyst with high loading capacity of active components.
The conventional petroleum resin hydrogenation modes comprise three modes, namely a slurry state, a fixed bed and a spray tower. The catalytic hydrogenation method for improving the petroleum resin is to dissolve the petroleum resin in solvents such as cyclohexane or mineral oil, load a nickel or aluminum catalyst on alumina or diatomite, introduce hydrogen at a high temperature to perform catalytic hydrogenation to reduce unsaturated double bonds, and finally, perform distillation and purification on a reaction product to obtain a high-purity petroleum resin product.
The supported palladium catalyst is one of the catalysts used in C5 petroleum resin industry at present, and the catalyst activity is closely related to the preparation method and the reaction conditions. The supported palladium catalyst has the characteristics of low hydrogenation degradation activity and high hydrogenated resin yield. Generally, when the palladium loading is less than or equal to 0.15 percent, the reaction temperature is above 290 ℃; even if the palladium supporting amount is 2%, the reaction temperature is required to be 280 ℃ or higher. The hydrogenation reaction of petroleum resin is affected by diffusion, and for Al with conventional pore diameter2O3The carrier and petroleum resin molecules are difficult to enter the interior of the catalyst particles, the active center on the surface of the catalyst plays a main role, and the active center in the particles has little effect. Therefore, the prepared ultrathin eggshell type catalyst is beneficial to reducing the diffusion influence and the dosage of Pd.
In addition, the research on the hydrogenation improvement catalyst of petroleum resin in China is not much, the production process is relatively laggard compared with that of developed countries in the west, and most petroleum resin products are imported, so the research on the hydrogenation improvement catalyst of the petroleum resin products is an important research direction for the development of China.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide an ultrathin eggshell type noble metal alloy catalyst for catalytic hydrogenation reaction of C5 petroleum resin, and a preparation method and application thereof, wherein noble metals Pd and Pt and Ca or Mg are loaded on Al2O3The surface of the material is formed to be thin like an eggshell, so that the exposure of active sites is facilitated, the rapid catalytic hydrogenation reaction of the C5 petroleum resin is facilitated, and the cost is reduced.
The ultrathin eggshell type noble metal alloy catalyst is characterized by comprising Al2O3A carrier, noble metal particles Pd and Pt and Ca or Mg, the noble metal particles Pd and Pt and Ca or Mg being supported on Al2O3The mass of Pd on the surface of the carrier is Al2O30.5-3% of the carrier.
The preparation method of the ultrathin eggshell type noble metal alloy catalyst is characterized by comprising the following specific steps of:
1）firstly, preparing a precursor aqueous solution, namely preparing H2PtCl6·6H2O、Na2PdCl4And nitrate are dissolved in deionized water and are uniformly mixed for standby;
2) putting the precursor aqueous solution prepared in the step 1) into a beaker, and adding Al2O3Stirring and mixing the materials uniformly, and adsorbing at room temperature;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and placing the obtained solid product in a muffle furnace for high-temperature calcination;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, roasting in the atmosphere of reducing gas, and after roasting is finished, obtaining a solid product, namely the ultrathin eggshell type noble metal alloy catalyst.
The preparation method of the ultrathin eggshell type noble metal alloy catalyst is characterized in that the nitrate in the step 1) is Mg (NO)3)2Or Ca (NO)3)2Wherein the mass ratio of Pd to Pt to Mg is 1:0.5-2:0.5-2 or the mass ratio of Pd to Pt to Ca is 1:0.5-2: 0.5-2.
The preparation method of the ultrathin eggshell type noble metal alloy catalyst is characterized in that Al in the step 2) is adopted2O3The volume ratio of the mass of the material to the precursor aqueous solution is 1:1.5-4, preferably 1:2.4, the volume unit is mL, the mass unit is g, and the adsorption time is 11.8-12.4 h.
The preparation method of the ultrathin eggshell type noble metal alloy catalyst is characterized in that the washing solvent in the step 3) is deionized water, the calcination temperature is 400-500 ℃, preferably 450 ℃, and the calcination time is 3.0-5.0 h.
The preparation method of the ultrathin eggshell type noble metal alloy catalyst is characterized in that the roasting temperature in the step 4) is 250-350 ℃, the roasting time is 2.0-5.0H, and the reducing gas is H2And N2In which H is2And N2The flow rate ratio of (A) is 1: 9-19.
The ultrathin eggshell type noble metal alloy catalyst is applied to hydrogenation reaction of C5 petroleum resin.
The application of the ultrathin eggshell type noble metal alloy catalyst is characterized by comprising the following specific steps:
mixing C5 petroleum resin solution and solvent in a reactor to obtain reaction liquid, adding ultrathin eggshell type noble metal alloy catalyst into the reaction liquid, carrying out continuous hydrogenation reaction in the atmosphere of hydrogen, separating reaction products by a gas-liquid separator at intervals to obtain a hydrogenated C5 petroleum resin compound, and measuring the unsaturation degree.
The application of the ultrathin eggshell type noble metal alloy catalyst is characterized in that the C5 petroleum resin is industrial grade and is not subjected to desulfurization and dechlorination treatment, wherein S is less than or equal to 150ppm, Cl is less than or equal to 200ppm, the initial bromine value is 22.68g/100mg, the solvent is cyclohexane, the reaction temperature is 250-300 ℃, the reaction pressure is 5.0-7.0MPa, the reactor is a fixed bed, and the space velocity is 500-1500h-1The concentration of the C5 petroleum resin solution is 5-20%, and the hydrogen-oil ratio is 400-600: 1.
The application of the ultrathin eggshell type noble metal alloy catalyst is characterized in that the unsaturation degree of the hydrogenated C5 petroleum resin compound is detected by GB/T24138-.
Compared with the prior art, the invention has the beneficial effects that:
1) by adopting the technical scheme of the invention, Pd, Pt, Ca or Mg are loaded on Al2O3The ultrathin eggshell-shaped noble metal alloy catalyst prepared from the material has the advantages that the thickness formed on the surface of the carrier is thin like an eggshell, the exposure of an active site is facilitated, and the catalyst shows excellent catalytic activity and service life when being applied to the hydrogenation reaction of C5 resin;
2) compared with the traditional supported noble metal catalyst, the catalyst has the Pd noble metal content of 0.5-3 percent, can complete hydrogenation reaction under the conditions of 250 ℃ and 6MPa when applied to the hydrogenation reaction of C5 petroleum resin, and has the bromine number of 0.04-1.28g/100mg and the activity duration of 49h after the catalytic hydrogenation reaction;
3) with general Al2O3Compared with noble metal-supported catalyst, the catalyst of the invention is prepared from Al2O3The catalyst of the invention enables the active component to be loaded on the surface of the carrier under the synergistic action of three metals, the loading capacity is low, so that the thickness of the active component is about 0.1mm, and the cost is effectively reduced under the condition of keeping the high-efficiency performance of the catalyst;
4) compared with the common single-component Pd hydrogenation catalyst, the catalyst of the invention adopts Pd-Pt alloy as the active component, the combination of the Pd-Pt alloy and the active component can effectively resist S, the addition of Ca or Mg can improve the resistance of the catalyst to Cl poison, and the stability and the service life of the catalyst are effectively improved.
Drawings
FIG. 1 is a diagram of the HTEM of catalyst 1 at 50nm in example 1 of the present invention;
FIG. 2 is a chart of HTEM at 10nm for catalyst 1 in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples, without however being limited to the scope of protection of the invention.
Example 1
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mg Mg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3 hours at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 1 after roasting is finished.
The analysis of the prepared catalyst 1 is shown in detail in FIG. 1, FIG. 2 and Table 1:
as can be seen from the transmission electron microscope (HTEM) images of fig. 1 and 2, the catalyst-supported noble metal Pd prepared in example 1 has a diameter of about 3 to 4nm and a dispersion degree is preferable.
Figure 24090DEST_PATH_IMAGE001
As is clear from Table 1, the contents of Pt, Pd and Mg were 0.96%, 0.97% and 0.97%, respectively, i.e., the mass ratio of Pd to Pt to Mg actually supported in the catalyst 1 was 1:1: 1.
2. The application of the catalyst 1 in the hydrogenation reaction of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 2
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) take 66.7mg of H2PtCl6·6H2O、69.5mg Na2PdCl4、268.8mg Mg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2Flow rate of 5ml/min and N2Roasting for 3 hours at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 2 after roasting is finished.
2. The application of the catalyst 2 in the hydrogenation reaction of the C5 petroleum resin is as follows:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 2 in the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2 And (3) carrying out continuous hydrogenation reaction in the atmosphere of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 3
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 399.9mg of H are taken2PtCl6·6H2O、416.7mg Na2PdCl4、1612.8mg Mg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2Flow rate of 5ml/min and N2Roasting for 3 hours at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 3 after roasting is finished.
2. The application of the catalyst 3 in the hydrogenation reaction of the C5 petroleum resin is as follows:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 3 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 4
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) take 66.7mg of H2PtCl6·6H2O、138.9mg Na2PdCl4、268.8mg Mg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3 hours at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 4 after roasting is finished.
2. The application of the catalyst 4 in the hydrogenation reaction of the C5 petroleum resin is as follows:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 4 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2The flow rate was 300ml/minThe continuous hydrogenation reaction is carried out in the atmosphere of (1), the reaction product is separated and taken out by a gas-liquid separator every 1h, and the unsaturation degree is measured.
Example 5
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 266.6mg of H are taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mg Mg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3 hours at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 5 after roasting is finished.
2. The application of the catalyst 5 in the hydrogenation reaction of the C5 petroleum resin is as follows:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 5 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 6
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、1075.2mgMg (NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2 Roasting for 3 hours at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 6 after roasting is finished.
2. The application of the catalyst 6 in the hydrogenation reaction of the C5 petroleum resin comprises the following steps:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 6 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1And C5 petroleum resin solution is continuously hydrogenated under the condition that the flow rate is 0.6ml/min and the flow rate of H2 is 300ml/min, reaction products are separated and taken out by a gas-liquid separator every 1H, and the unsaturation degree of the reaction products is measured.
Example 7
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、295.9mg Ca(NO3)2Dissolving 4H2O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3 hours at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 7 after roasting is finished.
2. The application of the catalyst 7 in the hydrogenation reaction of the C5 petroleum resin is as follows:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 7 in the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out a reaction product by a gas-liquid separator every 1h, and measuring the unsaturation degree, wherein the unsaturation degree is shown in table 2.
Figure 755286DEST_PATH_IMAGE002
As can be seen from Table 2, when the nitrate is Mg (NO)3)2In the case that the catalyst 1 prepared in example 1 had a catalytic activity lasting for 49 hours in the hydrogenation of the C5 petroleum resin, the resulting hydrogenated C5 petroleum resin compound had a bromine number of 0.04 to 1.28g/100g, and when the nitrate was Ca (NO) (i.e., a compound having a specific molecular weight of 0.04 to 1.28g/100 g)3)2In the case of the catalyst 7 prepared in example 7, the duration of the catalytic activity in the hydrogenation reaction of the C5 petroleum resin was short, the bromine number of the resulting hydrogenated C5 petroleum resin compound was 0.42 to 2.01, and the lower the bromine number, the better the hydrogenation effect of the C5 petroleum resin, and the better the product quality, so Mg (NO) was selected3)2Is superior.
Example 8
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 80mg of H is taken2PtCl6·6H2O、83.3mg Na2PdCl4、322.6mg Mg(NO3)2·6H2Dissolving O in 7.2mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 3gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3h at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 8 after roasting is finished.
2. The application of the catalyst 8 in the hydrogenation reaction of the C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 8 in the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 9
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 266.6mg of H are taken2PtCl6·6H2O、277.8mg Na2PdCl4、1075.2mg Mg(NO3)2·6H2Dissolving O in 24mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 10gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2Flow rate of 5ml/min and N2Roasting for 3h at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 9 after roasting is finished.
2. The application of the catalyst 9 in the hydrogenation reaction of the C5 petroleum resin is as follows:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 9 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 10
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mg Mg (NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 400 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2 Roasting for 3 hours at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 10 after roasting is finished.
2. The application of the catalyst 10 in the hydrogenation reaction of the C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 10 in the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 11
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mgMg (NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 500 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2Flow rate of 5ml/min and N2Roasting for 3h at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 11 after roasting is finished.
2. The application of the catalyst 11 in the hydrogenation reaction of the C5 petroleum resin is as follows:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 11 in the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 250 ℃, wherein-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2Carrying out continuous hydrogenation reaction at a flow rate of 300ml/min, and passing the reaction product through a reactor every 1hAnd (4) separating and taking out the mixture by a gas-liquid separator, and measuring the unsaturation degree of the mixture.
Example 12
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mgMg (NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 3 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2Flow rate of 5ml/min and N2Roasting for 3h at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 12 after roasting is finished.
2. Application of the catalyst 12 in hydrogenation reaction of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 12 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 13
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mg Mg(NO3)2·6H2O dissolved in 12mLUniformly mixing in deionized water for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 5 hours;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3 hours at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 13 after roasting is finished.
2. The application of the catalyst 13 in the hydrogenation reaction of the C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 13 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 14
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mgMg (NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3h at the roasting temperature of 300 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 14 after roasting is finished.
2. Application of the catalyst 14 in hydrogenation reaction of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 14 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 15
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mgMg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3 hours at the roasting temperature of 250 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 15 after roasting is finished.
2. The application of the catalyst 15 in the hydrogenation reaction of the C5 petroleum resin is as follows:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 15 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 16
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mg Mg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 2 hours at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 16 after roasting is finished.
2. Application of the catalyst 16 in hydrogenation reaction of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 16 in the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 250 ℃, wherein-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2Carrying out continuous hydrogenation reaction at a flow rate of 300ml/min, and carrying out gas-liquid reaction on the reaction product every 1hThe separator was separated and taken out, and the degree of unsaturation was measured.
Example 17
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mg Mg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 5 hours at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the catalyst 17 after roasting is finished.
2. The application of the catalyst 17 in the hydrogenation reaction of the C5 petroleum resin comprises the following steps:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 17 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 18
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mgMg (NO3)2·6H2O dissolved in 12mLMixing the mixture evenly in ionized water for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate 10ml/min and N2Roasting for 3h at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 90ml/min, and obtaining a solid product, namely the catalyst 18 after roasting is finished.
2. Application of the catalyst 18 in hydrogenation reaction of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 18 in the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 250 ℃, wherein-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 19
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mgMg (NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 7ml/min and N2Roasting for 3h at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 93ml/min, and obtaining a solid product, namely the catalyst 19 after roasting is finished.
2. Application of the catalyst 19 in hydrogenation reaction of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 19 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Comparison of the application conditions for catalyst 1 prepared in example 1
Example 20
Taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 280 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 21
Taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 300 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 22
Taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 5MPa and the space velocity of 1000h at the reaction temperature of 5MPa-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 23
Taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 7MPa and the space velocity of 1000h at the reaction temperature of 7MPa-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2 And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 24
Taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1C5 Petroleum resin solution flow rate of 0.75ml/min at H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 25
Taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.5ml/min under the condition of H2 Carrying out continuous hydrogenation reaction at a flow rate of 300ml/min, and reacting the reaction product every 1hAnd (4) separating and taking out the mixture through a gas-liquid separator, and measuring the unsaturation degree of the mixture.
Example 26
Taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.3ml/min under the condition of H2 And (3) carrying out continuous hydrogenation reaction at the flow rate of 150ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 27
Taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.9ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 450ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 28
Taking 50g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Example 29
Taking 200g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000%-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Comparative example 1
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) get 2.666g H2PtCl6·6H2O、2.778gNa2PdCl4、10.752gMg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3 hours at the flow rate of 95ml/min and the roasting temperature of 350 ℃, and obtaining a solid product, namely the comparative catalyst 1 after roasting is finished.
2. Application of comparative catalyst 1 in hydrogenation reaction of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a comparative catalyst 1 in the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000%-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Comparative example 2
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4Dissolving in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3 hours at the flow rate of 95ml/min and the roasting temperature of 350 ℃, and obtaining a solid product, namely the comparative catalyst 2 after roasting is finished.
2. Application of comparative catalyst 2 in hydrogenation reaction of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a comparative catalyst 2 in the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Comparative example 3
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、537.6mgMg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3 hours at the flow rate of 95ml/min and the roasting temperature of 350 ℃, and obtaining a solid product, namely the comparative catalyst 3 after roasting is finished.
2. Application of comparative catalyst 3 in hydrogenation reaction of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a comparative catalyst 3 in the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000%-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Comparative example 4
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、10.752g Mg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3 hours at the roasting temperature of 350 ℃ in the atmosphere of the flow rate of 95ml/min, and obtaining a solid product, namely the comparative catalyst 4 after roasting is finished.
2. Application of comparative catalyst 4 in hydrogenation of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a comparative catalyst 4 in the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000%-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2The continuous hydrogenation reaction was carried out at a flow rate of 300ml/min, and the reaction product was separated and taken out every 1 hour by a gas-liquid separator, and the degree of unsaturation was measured, as shown in tables 3 and 4.
Figure 66094DEST_PATH_IMAGE003
As can be seen from table 3, from example 2, example 1, example 3 and comparative example 1, when the loading amount of Pd is 0.5%, the duration of the activity of catalyst 2 is not changed significantly, but the bromine number of the generated hydrogenated C5 resin compound is high, which indicates that the catalyst 2 has poor catalytic hydrogenation effect in the C5 petroleum resin; when the loading of Pd is increased to 1%, the bromine number of the generated hydrogenated C5 resin compound is 0.04-1.28g/100g, the overall range is close to the bromine number when the loading of Pd is 3%, when the hydrogenation effect is increased to 20%, the hydrogenation effect is not changed significantly, but the cost is dozens of times, and the loading of Pd is preferably 1%.
Figure 820423DEST_PATH_IMAGE004
As can be seen from Table 4, from example 1 and example 4, when the mass of Pt and Mg is not changed, the mass of Pd is increased, the duration of the catalytic activity of the catalyst is obviously shortened, the bromine value of the product after catalytic hydrogenation is obviously increased, and the hydrogenation effect is deteriorated;
as can be seen from comparative example 3, example 1 and example 5, it can be seen from comparative example 3 that the catalyst is poisoned quickly without adding Pt because Pd-Pt has an S poisoning resistance; when the mass of Pd and Mg is not changed, the mass of Pt is increased, the duration time of the catalytic activity of the catalyst is obviously shortened, the bromine value of the product after catalytic hydrogenation is obviously increased, and the hydrogenation effect is poor;
as can be seen from comparative example 2, example 1, example 6 and comparative example 4, it can be seen from comparative example 2 that the duration of the catalyst activity is significantly shortened and the catalyst hydrogenation effect is poor without adding Mg, because the catalyst is deactivated by not adding Cl element in Mg petroleum resin; when the mass of Pd and Pt is unchanged, the mass of Mg is increased, the duration of the catalytic activity of the catalyst is shortened from 49h to 16h, the bromine value of the product after catalytic hydrogenation is increased from 0.04-1.28g/100g to 5.25-8.12g/100g, and the excessive amount of Mg can block the pore channels of the carrier and occupy the positions of the original active components, so that the activity of the catalyst is influenced, and the hydrogenation effect is reduced, and in conclusion, the mass ratio of Pd to Pt to Mg is preferably 1:1: 1.
Comparative example 5
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mgMg (NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 250 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3 hours at the flow rate of 95ml/min and the roasting temperature of 350 ℃, and obtaining a solid product, namely the comparative catalyst 5 after roasting is finished.
2. Application of comparative catalyst 5 in hydrogenation reaction of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, and fixingFilling a comparative catalyst 5 in the bed reactor, and controlling the reaction temperature at 250 ℃, the reaction pressure at 6MPa and the space velocity at 1000h-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Comparative example 6
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mg Mg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 5ml/min and N2Roasting for 3 hours at the flow rate of 95ml/min and the roasting temperature of 350 ℃, and obtaining a solid product, namely the comparative catalyst 6 after roasting is finished.
2. Application of comparative catalyst 6 in hydrogenation of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a comparative catalyst 6 in the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000%-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2The continuous hydrogenation reaction was carried out at a flow rate of 300ml/min, the reaction product was separated and taken out every 1h by a gas-liquid separator, and the degree of unsaturation was measured, as shown in Table 5.
Figure 557435DEST_PATH_IMAGE005
As can be seen from Table 5, the calcination temperature is 400-500 ℃, the activity duration of the catalyst is longer, the bromine number of the generated hydrogenated C5 resin compound is low, and the crystal form of alumina is converted into gamma; when the temperature is 250 ℃, the activity duration of the catalyst is short, the bromine number of the generated hydrogenated C5 resin compound is high, and the effect is poor because the crystal form of alumina is not completely converted into gamma; when the temperature is 1200 ℃, the crystal form of the alumina is completely converted into alpha, the pore diameter and the specific surface area are greatly reduced to cause the worst effect, and therefore 450 ℃ is preferred.
Comparative example 7
1. A preparation method of an ultrathin eggshell type noble metal alloy catalyst comprises the following steps:
1) 133.3mg of H was taken2PtCl6·6H2O、138.9mg Na2PdCl4、537.6mg Mg(NO3)2·6H2Dissolving O in 12mL of deionized water, and uniformly mixing for later use;
2) putting the precursor aqueous solution prepared in the step 1) into a 50mL beaker, and adding 5gAl2O3The materials are stirred and mixed to be uniform, and are placed at room temperature for adsorption for 12 hours;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and calcining the obtained solid product in a muffle furnace at 450 ℃ for 4 h;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, and performing high-temperature calcination in the presence of H2 Flow rate of 100ml/min and N2Roasting for 3 hours at the flow rate of 0ml/min and the roasting temperature of 350 ℃, and obtaining a solid product, namely the comparative catalyst 7 after roasting is finished.
2. Application of comparative catalyst 7 in hydrogenation of C5 petroleum resin:
taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a contrast catalyst 7 in the fixed bed reactor, and reacting at the reaction temperature of 250 DEG CThe pressure is 6MPa, and the space velocity is 1000h-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree, wherein the specific data are shown in Table 6.
Figure 143137DEST_PATH_IMAGE006
As is apparent from Table 6, from examples 1, 19 and 18, it is seen that the duration of the catalytic activity is not greatly changed and the catalytic hydrogenation effect is slightly deteriorated, possibly due to the occurrence of hydrogen flooding, as a result of increasing the content of hydrogen in the mixed hydrogen-nitrogen gas, and from comparative example 7, it is seen that the duration of the catalytic activity is shortened by using pure hydrogen for the catalytic hydrogenation, and that the use of pure hydrogen in the hydrogenation reaction of C5 petroleum resin is more costly and dangerous than the use of the mixed hydrogen-nitrogen gas, so H is preferable2And N2The flow rate of (3) was 1: 19.
Comparative example 8
Taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 200 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Comparative example 9
Taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 4MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 0.6ml/min under the condition of H2 And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Comparative example 10
Taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1C5 Petroleum resin solution flow rate of 3ml/min at H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 300ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Comparative example 11
Taking 150g of C5 petroleum resin and 1L of cyclohexane, uniformly mixing in a 1.5L raw material tank to obtain a reaction solution, pumping the reaction solution into a fixed bed reactor through a raw material pump, filling a catalyst 1 into the fixed bed reactor, and reacting at the temperature of 250 ℃, the reaction pressure of 6MPa and the space velocity of 1000h at the reaction temperature of 1000 DEG C-1The flow rate of the C5 petroleum resin solution is 1.8ml/min, and the reaction is carried out under the condition of H2And (3) carrying out continuous hydrogenation reaction at the flow rate of 900ml/min, separating and taking out reaction products every 1h by using a gas-liquid separator, and measuring the unsaturation degree of the reaction products.
Comparative example 12
250g of C5 petroleum resin and 1L of cyclohexane are uniformly mixed in a 1.5L raw material tank to obtain a reaction solution, the reaction solution is pumped into a fixed bed reactor through a raw material pump, a catalyst 1 is filled in the fixed bed reactor, continuous hydrogenation reaction is carried out under the conditions that the reaction temperature is 250 ℃, the reaction pressure is 6MPa, the space velocity is 1000H < -1 >, and the flow velocity of the C5 petroleum resin solution is 0.6ml/min, the flow velocity of H2 is 300ml/min, reaction products are separated and taken out through a gas-liquid separator every 1H, the unsaturation degree of the reaction products is measured, and specific data are shown in Table 7.
Figure 572981DEST_PATH_IMAGE007
As can be seen from table 7, from example 1, example 20, example 21 and comparative example 8, the hydrogenation reaction did not occur when the reaction temperature was 200 ℃; when the reaction temperature is 250 ℃, the activity duration time of the catalyst is 49h, the bromine number of the product after catalytic hydrogenation is 0.04-1.28g/100g, the activity duration time and the catalytic effect of the catalyst are not obviously changed along with the rise of the temperature, and 250 ℃ is selected as the appropriate reaction temperature in consideration of the cost;
from comparative example 9, example 22, example 1 and example 23, it is understood that the hydrogenation reaction did not occur when the reaction pressure was 4 MPa; when the reaction pressure is more than 5MPa, the activity duration of the catalyst is slightly increased, the bromine number of the product after the catalyst is hydrogenated is slightly reduced, and 6MPa is selected as the appropriate reaction pressure in consideration of the cost;
the space velocity is a measure of the ability of the catalyst to process the reaction gas per unit time, and it can be seen from comparative example 12, example 27, example 1 and example 26 that the duration of the catalyst activity does not change much as the space velocity increases, but the bromine number of the product after catalytic hydrogenation is slightly increased from a large value to a small value, so 1000 hours are selected-1Is suitable space velocity;
the hydrogen-oil ratio reflects the petroleum resin processing capacity of the catalyst in unit time, and as seen from comparative example 10, example 24, example 1 and example 25, when the hydrogen-oil ratio is 100:1, because the solution flow rate is too fast and is far greater than the instantaneous processing capacity of the catalyst, the hydrogenation reaction does not occur, the hydrogenation effect of the catalyst is obviously improved along with the increase of the hydrogen-oil ratio, when the hydrogen-oil ratio is 600:1, the catalytic hydrogenation effect has no obvious change, the comprehensive consideration cost is high, and 500:1 is selected as the proper hydrogen-oil ratio;
as can be seen from examples 28, 29 and 12, the catalytic hydrogenation effect is obviously reduced along with the increase of the concentration of the C5 petroleum resin, and when the concentration is 5%, the bromine number of the product of the C5 petroleum resin after hydrogenation is low, which shows that the catalyst hydrogenation effect is better;
in conclusion, the reaction temperature is 250 ℃, the reaction pressure is 6MPa, and the space velocity is 1000h-1Hydrogen-oil ratio 500: 1. a suitable reaction condition was C5 petroleum resin concentration of 5%.

Claims (10)

1. An ultrathin eggshell type noble metal alloy catalyst is characterized in that the catalyst comprises Al2O3A carrier, noble metal particles Pd and Pt and Ca or Mg, the noble metal particles Pd and Pt and Ca or Mg being supported on Al2O3The mass of Pd on the surface of the carrier is Al2O30.5-3% of the carrier.
2. A method for preparing the ultra-thin eggshell noble metal alloy catalyst as recited in claim 1, which comprises the following steps:
1) firstly, preparing a precursor aqueous solution, namely preparing H2PtCl6·6H2O、Na2PdCl4And nitrate are dissolved in deionized water and are uniformly mixed for standby;
2) putting the precursor aqueous solution prepared in the step 1) into a beaker, and adding Al2O3Stirring and mixing the materials uniformly, and adsorbing at room temperature;
3) after the adsorption in the step 2) is finished, carrying out suction filtration and washing on the reaction product, and placing the obtained solid product in a muffle furnace for high-temperature calcination;
4) after the high-temperature calcination in the step 3), placing the obtained high-temperature calcination product in a tube furnace, roasting in the atmosphere of reducing gas, and after roasting is finished, obtaining a solid product, namely the ultrathin eggshell type noble metal alloy catalyst.
3. The method for preparing an ultra-thin eggshell type noble metal alloy catalyst as claimed in claim 2, wherein the nitrate in step 1) is Mg (NO)3)2Or Ca (NO)3)2Wherein the mass ratio of Pd to Pt to Mg is 1:0.5-2:0.5-2 or the mass ratio of Pd to Pt to Ca is 1:0.5-2: 0.5-2.
4. The method for preparing an ultra-thin eggshell type noble metal alloy catalyst as claimed in claim 2, wherein Al in step 2)2O3The volume ratio of the mass of the material to the precursor aqueous solution is 1:1.5-4, preferably 1:2.4, the volume unit is mL, the mass unit is g, and the adsorption time is 11.8-12.4 h.
5. The method for preparing an ultra-thin eggshell type noble metal alloy catalyst as claimed in claim 2, wherein the washing solvent in step 3) is deionized water, the calcination temperature is 400-500 ℃, preferably 450 ℃, and the calcination time is 3.0-5.0 h.
6. The method for preparing the ultra-thin eggshell type noble metal alloy catalyst as claimed in claim 2, wherein the calcination temperature in the step 4) is 250-350 ℃, the calcination time is 2.0-5.0H, and the reducing gas is H2And N2In which H is2And N2The flow rate ratio of (A) is 1: 9-19.
7. Use of the ultra-thin eggshell noble metal alloy catalyst of claim 1 in hydrogenation of C5 petroleum resin.
8. Use of an ultra-thin eggshell noble metal alloy catalyst as claimed in claim 7, characterized in that it comprises the steps of:
mixing C5 petroleum resin solution and solvent in a reactor to obtain reaction liquid, adding ultrathin eggshell type noble metal alloy catalyst into the reaction liquid, carrying out continuous hydrogenation reaction in the atmosphere of hydrogen, separating reaction products by a gas-liquid separator at intervals to obtain a hydrogenated C5 petroleum resin compound, and measuring the unsaturation degree.
9. The use of the ultra-thin eggshell-type noble metal alloy catalyst as claimed in claim 8, wherein the C5 petroleum resin is technical grade, and has not undergone desulfurization and dechlorination treatment, wherein S is less than or equal to 150ppm, Cl is less than or equal to 200ppm, the initial bromine number is 22.68g/100mg, the solvent is cyclohexane, the reaction temperature is 250-300 ℃, the reaction pressure is 5.0-7.0MPa, the reactor is a fixed bed, and the space velocity is 500-1500h-1The concentration of the C5 petroleum resin solution is 5-20%, and the hydrogen-oil ratio is 400-600: 1.
10. Use of the ultra-thin eggshell noble metal alloy catalyst as claimed in claim 8 wherein said hydrogenated C5 petroleum resin compound is tested for unsaturation by GB/T24138-.
CN202011039259.9A 2020-09-28 2020-09-28 Ultrathin eggshell type noble metal alloy catalyst for catalytic hydrogenation reaction of C5 petroleum resin and preparation method and application thereof Pending CN112191245A (en)

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