CN109865519B - Ruthenium modified activated carbon supported nickel catalyst, preparation method and application thereof - Google Patents

Ruthenium modified activated carbon supported nickel catalyst, preparation method and application thereof Download PDF

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CN109865519B
CN109865519B CN201711249038.2A CN201711249038A CN109865519B CN 109865519 B CN109865519 B CN 109865519B CN 201711249038 A CN201711249038 A CN 201711249038A CN 109865519 B CN109865519 B CN 109865519B
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nickel
activated carbon
cyclopentadiene
ruthenium
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CN109865519A (en
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李泽壮
刘经伟
方晓江
杨爱武
季松
柏基业
刘丽娟
王英武
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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Sinopec Yangzi Petrochemical Co Ltd
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Abstract

The invention discloses a ruthenium modified activated carbon supported nickel catalyst, a preparation method and an application thereof. The acidic functional group carboxyl on the surface of the activated carbon is modified by silylation, and the organic functional group is used for replacing H playing an acidic role in the carboxyl, so that the acidity of the surface of the catalyst is reduced, and the reaction performance of the catalyst is improved; meanwhile, an auxiliary agent Ru is introduced into the activated carbon supported nickel catalyst to improve the dispersion degree of Ni metal particles and enhance the activity of the catalyst; the catalyst is applied to cyclopentadiene gas phase selective hydrogenation to prepare cyclopentene, the conversion rate of cyclopentadiene is 91-100%, and the selectivity of cyclopentene is 85-98%.

Description

Ruthenium modified activated carbon supported nickel catalyst, preparation method and application thereof
Technical Field
The invention relates to a ruthenium modified activated carbon supported nickel catalyst, a preparation method and application thereof, belonging to the field of cyclopentadiene gas phase selective hydrogenation preparation.
Background
The cyclopentene can be used for producing various fine chemicals with high added values, and the chemicals are widely applied to the fields of pharmaceutical industry, organic synthesis, synthetic rubber and the like. Cyclopentanol prepared from cyclopentene can be used for producing pharmaceutical intermediates and perfumes, and is a raw material for preparing cyclopentanone, bromocyclopentane, chlorocyclopentane, drug cyclopentacarnethazine and anesthetic ketamine. Cyclopentanone is a raw material for preparing jasmine ketone spices, anxiolytic buspirone and pesticide bactericide pencycuron, and in addition, because the cyclopentanone has good solubility to various resins, the cyclopentanone can be widely used as a cleaning agent and a solvent in the electronic industry. Glutaraldehyde prepared from cyclopentene is excellent tanning agent, tissue curing agent, protein cross-linking agent and high-efficiency bactericidal disinfectant, and can be widely used in medicine and health, leather industry, petroleum industry, food industry, etc. Cyclopentene methyl ether prepared from cyclopentene is an excellent solvent, and can replace organic solvents such as tetrahydrofuran, methyl tert-butyl ether and the like. Cyclopentane prepared from cyclopentene can be used as refrigerator refrigerant instead of chlorofluorocarbon, and also can be used as solvent in solution polymerization of polyisoprene rubber and the like. Glutaric acid prepared from cyclopentene can be widely applied in the aspects of chemistry, construction, medicine, agriculture and the like. Heptafluorocyclopentane, octafluorocyclopentene and the like prepared from cyclopentene are pollution-free, almost have zero damage to an ozone layer, and are green, safe and environment-friendly materials.
The synthesis method of cyclopentene mainly has three methods: (1) the early method comprises the following steps: the cyclopentanol is prepared by gas phase dehydration at 380-400 ℃ by using alumina as a catalyst, but the cyclopentanol cannot be produced in large scale by the method because of limited sources; (2) BASF-Erdchemie method: heating the by-product C5 fraction as raw material to dimerize cyclopentadiene into dicyclopentadiene, extracting with N-methyl pyrrolidone, cracking to obtain cyclopentadiene, selectively hydrogenating to obtain cyclopentene, adding into cyclopentadiene-containing material, extracting, distilling and fractionating to obtain cyclopentene and isoprene. The method has long process and complex working procedure; (3) bayer process: the C5 fraction is heat treated to obtain dicyclopentadiene, which is then depolymerized to cyclopentadiene and finally hydrogenated to cyclopentene by catalysis, palladium catalyst, Cr or Ti as cocatalyst and Li-Al spinel as carrier are used.
The process for preparing cyclopentene by cyclopentadiene selective hydrogenation can be divided into gas phase hydrogenation and liquid phase hydrogenation. At present, the cyclopentene is industrially produced mainly by a liquid-phase hydrogenation process, and although the process can obtain high yield of the cyclopentene, the catalyst is difficult to recover, continuous production cannot be realized, and the reaction pressure is high. The gas phase hydrogenation process can be operated under normal pressure and can be continuously produced, but has the defects of complex catalyst preparation, short service life or low activity. The focus of developing gas phase hydrogenation processes is therefore on the development of catalysts.
The catalyst for preparing cyclopentene by gas-phase selective hydrogenation of cyclopentadiene mainly comprises palladium catalyst and nickel catalyst, wherein the palladium catalyst is expensive and is easily oxidized and inactivated in air at normal temperature. The nickel catalyst is low in price and mainly comprises Raney Ni, supported crystalline nickel and a supported amorphous nickel catalyst, wherein the Raney Ni catalyst is complex to prepare, the supported crystalline nickel catalyst is low in hydrogenation activity, and the supported amorphous nickel catalyst is high in hydrogenation activity, so that the nickel catalyst is a nickel catalyst which is mainly developed.
The Pd/C hydrogenation catalyst commonly used in industry at present takes active carbon as a carrier. The activated carbon has a high specific surface area and a rich pore structure. However, the surface of the activated carbon contains rich acidic oxygen-containing functional groups, such as carboxyl, carboxylic anhydride and lactone group, wherein the carboxyl is the most acidic, the lactone group is the second, and the phenolic hydroxyl is weakly acidic. The study shows that the acidity of the catalyst surface is unfavorable for the hydrogenation reaction, and the common modification method is to add an alkaline auxiliary agent into the catalyst. But the addition of the auxiliary agent can reduce the dispersion degree of the active metal on the surface of the carrier and reduce the reaction performance of the catalyst.
Disclosure of Invention
The invention provides a ruthenium modified activated carbon supported nickel catalyst, a preparation method and application thereof. Meanwhile, an auxiliary agent Ru is introduced into the activated carbon supported nickel catalyst to improve the dispersion degree of Ni metal particles and enhance the activity of the catalyst.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a ruthenium modified activated carbon supported nickel catalyst comprises 10-20 wt% of nickel, 0.5-1.5wt% of ruthenium and the balance of activated carbon.
The applicant researches and discovers that the introduction of a small amount of ruthenium into the nickel-based hydrogenation catalyst can reduce the reduction degree of NiO and improve the dispersion degree of Ni metal particles, and the high-dispersion Ni metal particles are beneficial to improving the hydrogenation activity of the catalyst and have a certain inhibiting effect on sintering and carbon deposition. wt means weight percent.
The preparation method of the ruthenium modified activated carbon supported nickel catalyst comprises the following steps of:
(1) putting activated carbon in a solvent, and carrying out ultrasonic oscillation;
(2) slowly dropwise adding a silylation reagent into the material obtained in the step (1) under the stirring condition;
(3) performing ultrasonic oscillation on the material obtained in the step (2) at high frequency;
(4) carrying out suction filtration on the material obtained in the step (3), washing the obtained solid with alcohol, and drying under a vacuum condition;
(5) preparing a nickel salt aqueous solution;
(6) putting the material obtained in the step (4) into the nickel salt solution obtained in the step (5), and stirring and dipping the material at the room temperature in the same volume;
(7) drying the solid in the material obtained in the step (6);
(8) preparing a ruthenium chloride aqueous solution;
(9) putting the material obtained in the step (7) into the ruthenium chloride aqueous solution obtained in the step (8), and stirring and dipping the material in the same volume at room temperature;
(10) and (4) drying, calcining and pre-reducing the solid in the material obtained in the step (9) to obtain the ruthenium modified activated carbon supported nickel catalyst.
In the step (1), the solvent is benzene, ether or perchloroethylene, and the dosage of the activated carbon relative to the solvent is 0.15-0.35 g/mL. This further improves the reactivity of the resulting catalyst.
In the step (2), the silylation reagent is at least one of trimethylchlorosilane, triethylchlorosilane or trimethoxychlorosilane, the volume-to-mass ratio of the silylation reagent to the activated carbon is 0.1-0.5mL/g, and the dropping rate of the silylation reagent is 0.3-1 mL/min. This further improves the reactivity of the resulting catalyst.
In the step (3), the ultrasonic oscillation time under high frequency is 1.5-4h, and the frequency is 1.7-2.4 MHZ; in the step (4), the alcohol washing reagent is absolute methanol or absolute ethanol; the drying temperature is 100-150 ℃, and the drying time is 4-10 h. This further improves the reactivity of the resulting catalyst.
In the step (5), the nickel salt is nickel nitrate, nickel acetate or nickel chloride, and the concentration of nickel in the nickel salt is 0.086-0.196 g/mL; and (4) soaking for 3-6h in the step (6) and the step (9). This further improves the reactivity of the resulting catalyst.
In the step (8), the concentration of ruthenium is 0.004-0.015 g/mL. This further increases the hydrogenation activity of the catalyst.
In the step (10), the drying temperature is 100-150 ℃, and the time is 3-6 h; the calcining atmosphere is nitrogen or argon, the temperature is 400-500 ℃, and the time is 3-7 h; the pre-reduction adopts hydrogen as reducing gas, the reduction temperature is 400-500 ℃, and the reduction time is 4-8 h. This further increases the hydrogenation activity of the catalyst.
When the catalyst is applied to cyclopentadiene gas phase selective dehydrogenation for preparing cyclopentene, the reaction temperature is 90-130 ℃, the hydrogen-hydrocarbon ratio is 0.8-1.2, and the liquid space velocity of cyclopentadiene is 4-9h-1. The conversion rate of cyclopentadiene is 91-100%, and the selectivity of cyclopentene is 85-98%.
When the catalyst is applied to the gas phase selective dehydrogenation of cyclopentadiene to prepare cyclopentene, the used device comprises: ice bath, cyclopentadiene storage tank, metering pump and high-purity H2Steel cylinder, high purity N2Steel bottle, first mass flowmeter, second mass flowmeter, first air-vent valve, second air-vent valve, reaction tube, conduction oil heating furnaceThe heat exchanger, the high-temperature circulator, the condensing tank and the gas-liquid separation tank; the cyclopentadiene storage tank is arranged in the ice bath, and the cyclopentadiene storage tank, the metering pump and the reaction tube are communicated in sequence through pipelines; high purity H2The steel cylinder, the first mass flowmeter, the first pressure regulating valve and the reaction tube are communicated in sequence through a pipeline; high purity N2The steel cylinder, the second mass flowmeter, the second pressure regulating valve and the reaction pipe are communicated in sequence through a pipeline; the reaction tube is arranged in the heat-conducting oil heating furnace, and the heat-conducting oil heating furnace, the heat exchanger, the high-temperature circulator and the heat-conducting oil heating furnace are sequentially communicated through pipelines to form circulation; the reaction tube, the condensing tank and the gas-liquid separation tank are communicated in sequence through pipelines;
the reaction tube is heated by heat-conducting oil, the heat-conducting oil is heated and circulated by the high-temperature circulator, the heat-conducting oil absorbing the exothermic reaction is removed by the heat exchanger, and the exothermic rapid transfer of the catalyst can be realized by adjusting the flow rate and the heat exchange rate of the heat-conducting oil, so that the aim of continuously controlling the reaction temperature of the catalyst is fulfilled; the method for preparing cyclopentene by gas-phase selective hydrogenation of cyclopentadiene comprises the steps of filling a catalyst in a reaction tube, introducing high-purity nitrogen, opening a high-temperature circulator to circularly heat conduction oil to a set temperature, then starting pumping cyclopentadiene for reaction, adjusting the flow rate and the heat exchange rate of the conduction oil to maintain the reaction temperature at the set temperature, then emptying a gas-liquid separation tank, collecting products again, carrying out gas-phase analysis on the newly collected products after stable reaction for 0.5h, and switching feed gas from high-purity hydrogen to high-purity nitrogen after the reaction is finished.
The condensing tank is provided with a condensate inlet and a condensate outlet which are arranged from bottom to top; the gas-liquid separation tank is provided with a liquid discharge hole.
The prior art is referred to in the art for techniques not mentioned in the present invention.
According to the ruthenium modified activated carbon supported nickel catalyst, acidic functional groups on the surface of activated carbon are subjected to silylation modification, and organic functional groups are used for replacing H playing an acidic role in carboxyl, so that the acidity of the surface of the catalyst is reduced, and the reaction performance of the catalyst is improved; meanwhile, an auxiliary agent Ru is introduced into the activated carbon supported nickel catalyst to improve the dispersion degree of Ni metal particles and enhance the activity of the catalyst.
Drawings
FIG. 1 is a schematic diagram of a cyclopentadiene gas-phase selective hydrogenation cyclopentene preparation device according to the present application;
in the figure, 1 ice bath, 2 cyclopentadiene storage tanks, 3 metering pumps and 4 high-purity H2A steel cylinder, 5 first pressure regulating valves, 6 first mass flowmeters and 7 high-purity N2The device comprises a steel cylinder, 8 second pressure regulating valves, 9 second mass flowmeters, 10 reaction tubes, 11 heat conducting oil heating furnaces, 12 heat exchangers, 13 high-temperature circulators and 14 condensate inlets; 15 a condensate outlet; 16 condensation tanks and 17 tail gas outlets; 18 a gas-liquid separation tank; 19 a liquid outlet.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In each example, when the catalyst is applied to the gas phase selective dehydrogenation of cyclopentadiene to prepare cyclopentene, the device used is as shown in fig. 1, and comprises: ice bath, cyclopentadiene storage tank, metering pump and high-purity H2Steel cylinder, high purity N2The device comprises a steel cylinder, a first mass flowmeter, a second mass flowmeter, a first pressure regulating valve, a second pressure regulating valve, a reaction tube, a heat conducting oil heating furnace, a heat exchanger, a high-temperature circulator, a condensing tank and a gas-liquid separation tank; the cyclopentadiene storage tank is arranged in the ice bath, and the cyclopentadiene storage tank, the metering pump and the reaction tube are communicated in sequence through pipelines; high purity H2The steel cylinder, the first mass flowmeter, the first pressure regulating valve and the reaction tube are communicated in sequence through a pipeline; high purity N2The steel cylinder, the second mass flowmeter, the second pressure regulating valve and the reaction pipe are communicated in sequence through a pipeline; the reaction tube is arranged in the heat-conducting oil heating furnace, and the heat-conducting oil heating furnace, the heat exchanger, the high-temperature circulator and the heat-conducting oil heating furnace are sequentially communicated through pipelines to form circulation; the reaction tube, the condensing tank and the gas-liquid separation tank are communicated in sequence through pipelines;
the reaction tube is heated by heat-conducting oil, the heat-conducting oil is heated and circulated by the high-temperature circulator, the heat-conducting oil absorbing the exothermic reaction is removed by the heat exchanger, and the exothermic rapid transfer of the catalyst can be realized by adjusting the flow rate and the heat exchange rate of the heat-conducting oil, so that the aim of continuously controlling the reaction temperature of the catalyst is fulfilled; the method for preparing cyclopentene by gas-phase selective hydrogenation of cyclopentadiene comprises the steps of filling a catalyst in a reaction tube, introducing high-purity nitrogen, opening a high-temperature circulator to circularly heat conduction oil to a set temperature, then starting pumping cyclopentadiene for reaction, adjusting the flow rate and the heat exchange rate of the conduction oil to maintain the reaction temperature at the set temperature, then emptying a gas-liquid separation tank, collecting products again, carrying out gas-phase analysis on the newly collected products after stable reaction for 0.5h, and switching feed gas from high-purity hydrogen to high-purity nitrogen after the reaction is finished.
The room temperature in each case was 25 ℃ and the stirring speed was 60 revolutions per minute.
Example 1
12g of activated carbon was placed in 80mL of diethyl ether and shaken ultrasonically at 0.5MHZ for 10 min. Under the condition of stirring, 1.2mL of triethylchlorosilane is slowly dripped into the liquid, and the dripping speed is 0.3 mL/min. The liquid is placed in an ultrasonic cleaner and is subjected to ultrasonic oscillation for 1.5h at 1.7 MHZ. The liquid was filtered with suction, the solid was washed with anhydrous methanol and then dried at 100 ℃ for 4h under vacuum. 13mL of nickel chloride aqueous solution having a nickel concentration of 0.086g/mL was prepared. 10g of dried activated carbon is put into a nickel salt solution and soaked for 3 hours under equal volume stirring at room temperature. The solid was dried at 100 ℃ for 3 h. 13mL of an aqueous ruthenium chloride solution having a ruthenium concentration of 0.004g/mL was prepared. Putting the activated carbon loaded with nickel into a ruthenium chloride aqueous solution, and soaking for 3h at room temperature under equal volume stirring. Drying the solid at 100 ℃ for 3h, calcining the solid at 400 ℃ for 3h in a nitrogen atmosphere, and finally pre-reducing the solid at 400 ℃ for 4h in a hydrogen atmosphere to obtain the ruthenium modified activated carbon supported nickel catalyst with the nickel loading of 10% and the ruthenium loading of 0.5%.
Filling 5mL of the prepared catalyst into a reaction tube, introducing hydrogen at the hydrogen flow rate of 6.51L/h, opening a high-temperature circulator to circularly heat conduction oil to 86 ℃, then starting pumping cyclopentadiene for reaction, wherein the cyclopentadiene flow rate is 20mL/h (16g/h), adjusting the heat conduction oil flow rate and the heat exchange rate to keep the reaction temperature at 90 ℃, then emptying a gas-liquid separation tank, collecting the product again, and after stable reaction for 0.5h, performing gas phase analysis on the newly collected product. The results show that at a reaction temperature of 90 ℃ the hydrogen to hydrocarbon ratio is 1.2, cyclicLiquid volume space velocity of pentadiene is 4h-1Under the conditions, the conversion rate of cyclopentadiene was 91%, and the selectivity of cyclopentene was 85%.
Example 2:
14g of activated carbon was placed in 40mL of perchloroethylene and shaken ultrasonically at 0.5MHZ for 10 min. Under the condition of stirring, slowly dripping 7mL of trimethoxy chlorosilane into the liquid at the dripping speed of 1 mL/min. The liquid is placed in an ultrasonic cleaner and is subjected to ultrasonic oscillation for 4 hours at 2.0 MHZ. Filtering the liquid, washing the solid with absolute ethyl alcohol, and then vacuumizing and drying at 150 ℃ for 10 h. 13mL of nickel acetate aqueous solution having a nickel concentration of 0.196g/mL was prepared. 10g of dried activated carbon is put into a nickel salt solution and immersed for 6 hours under equal volume stirring at room temperature. The solid was dried at 150 ℃ for 6 h. 13mL of an aqueous ruthenium chloride solution having a ruthenium concentration of 0.015g/mL was prepared. Putting the activated carbon loaded with nickel into a ruthenium chloride aqueous solution, and soaking for 6h at room temperature under equal volume stirring. Drying the solid at 150 ℃ for 6h, calcining the solid at 500 ℃ for 7h in a nitrogen atmosphere, and finally pre-reducing the solid at 450 ℃ for 8h in a hydrogen atmosphere to obtain the ruthenium modified activated carbon supported nickel catalyst with 20% of nickel load and 1.5% of ruthenium load.
Filling 5mL of the prepared catalyst into a reaction tube, introducing hydrogen at a hydrogen flow rate of 9.76L/h, opening a high-temperature circulator to circularly heat conduction oil to 122 ℃, then starting pumping cyclopentadiene for reaction, wherein the cyclopentadiene flow rate is 45mL/h (36g/h), adjusting the heat conduction oil flow rate and the heat exchange rate to keep the reaction temperature at 130 ℃, then emptying a gas-liquid separation tank, collecting the product again, and after stable reaction for 0.5h, performing gas phase analysis on the newly collected product. The results show that at the reaction temperature of 130 ℃, the hydrogen-hydrocarbon ratio of 0.8 and the liquid space velocity of cyclopentadiene of 9h-1Under the conditions, the conversion rate of cyclopentadiene is 100%, and the selectivity of cyclopentene is 89%.
Example 3:
10g of activated carbon was placed in 40mL of benzene and shaken ultrasonically at 0.5MHZ for 10 min. Under the condition of stirring, 4mL of trimethylchlorosilane is slowly dripped into the liquid, and the dripping speed is 0.8 mL/min. The liquid is placed in an ultrasonic cleaning instrument and is subjected to ultrasonic oscillation for 2 hours at 2.3 MHZ. Filtering the liquid, washing the solid with absolute ethyl alcohol, and then vacuumizing and drying for 6h at 120 ℃. 13mL of a nickel nitrate aqueous solution having a nickel concentration of 0.148g/mL was prepared. 10g of dried activated carbon is put into a nickel salt solution and immersed for 4 hours under equal volume stirring at room temperature. The solid was dried at 120 ℃ for 4 h. 13mL of an aqueous ruthenium chloride solution having a ruthenium concentration of 0.0093g/mL was prepared. Putting the activated carbon loaded with nickel into a ruthenium chloride aqueous solution, and soaking for 4h at room temperature under equal volume stirring. Drying the solid at 120 ℃ for 4h, calcining the solid at 500 ℃ for 5h in a nitrogen atmosphere, and finally pre-reducing the solid at 500 ℃ for 5h in a hydrogen atmosphere to obtain the ruthenium modified activated carbon supported nickel catalyst with 16% of nickel load and 1% of ruthenium load.
Filling 5mL of the prepared catalyst into a reaction tube, introducing hydrogen at a hydrogen flow rate of 9.49L/h, opening a high-temperature circulator to circularly heat conduction oil to 114 ℃, then starting pumping cyclopentadiene for reaction, wherein the cyclopentadiene flow rate is 35mL/h (28g/h), adjusting the heat conduction oil flow rate and the heat exchange rate to maintain the reaction temperature at 120 ℃, then emptying a gas-liquid separation tank, collecting the product again, and after stable reaction for 0.5h, performing gas phase analysis on the newly collected product. The results show that at the reaction temperature of 120 ℃, the hydrogen-hydrocarbon ratio of 1.0 and the liquid space velocity of cyclopentadiene of 7h-1Under the conditions, the conversion rate of cyclopentadiene is 100%, and the selectivity of cyclopentene is 98%.
Example 4:
filling 5mL of the catalyst prepared in the embodiment 3 in a reaction tube, introducing hydrogen at a hydrogen flow rate of 9.49L/h, opening a high-temperature circulator to circularly heat conduction oil to 121 ℃, then starting pumping cyclopentadiene for reaction, adjusting the flow rate of the conduction oil and the heat exchange rate to keep the reaction temperature at 128 ℃, then emptying a gas-liquid separation tank, collecting the product again, and after stable reaction for 0.5h, performing gas phase analysis on the newly collected product. The results show that at the reaction temperature of 128 ℃, the hydrogen-hydrocarbon ratio of 1.0 and the liquid space velocity of cyclopentadiene of 7h-1Under the conditions, the conversion rate of cyclopentadiene was 100%, and the selectivity of cyclopentene was 94.2%.
Example 5:
5mL of the catalyst prepared in the example 3 is filled in a reaction tube, hydrogen is introduced at the hydrogen flow rate of 9.49L/h, a high-temperature circulator is opened to circularly heat the heat-conducting oil to 91 ℃, and then the cyclopentyl is pumpedDiene reaction, namely, the flow rate of cyclopentadiene is 35mL/h (28g/h), the flow rate of heat conduction oil and the heat exchange rate are adjusted to maintain the reaction temperature at 97 ℃, then the gas-liquid separation tank is emptied, the product is collected again, and after the stable reaction is carried out for 0.5h, the gas phase analysis is carried out on the newly collected product. The results show that at the reaction temperature of 97 ℃, the hydrogen-hydrocarbon ratio of 1.0 and the liquid space velocity of cyclopentadiene of 7h-1Under the conditions, the conversion rate of cyclopentadiene was 94.7%, and the selectivity of cyclopentene was 96.2%.
Example 6:
filling 5mL of the catalyst prepared in the embodiment 3 in a reaction tube, introducing hydrogen at the hydrogen flow rate of 11.39L/h, opening a high-temperature circulator to circularly heat conduction oil to 114 ℃, then starting pumping cyclopentadiene for reaction, adjusting the flow rate of the conduction oil and the heat exchange rate to maintain the reaction temperature at 121 ℃ and then emptying a gas-liquid separation tank, collecting the product again, and after stable reaction for 0.5h, performing gas phase analysis on the newly collected product. The results show that at the reaction temperature of 121 ℃, the hydrogen-hydrocarbon ratio of 1.2 and the liquid space velocity of cyclopentadiene of 7h-1Under the conditions, the conversion rate of cyclopentadiene was 100%, and the selectivity of cyclopentene was 93.8%.
Example 7:
filling 5mL of the catalyst prepared in the embodiment 3 in a reaction tube, introducing hydrogen at a flow rate of 12.20L/h, opening a high-temperature circulator to circularly heat conduction oil to 117 ℃, then starting pumping cyclopentadiene for reaction at a flow rate of 45mL/h (36g/h), adjusting the flow rate of the conduction oil and the heat exchange rate to maintain the reaction temperature at 120 ℃, then emptying a gas-liquid separation tank, collecting the product again, and after stable reaction for 0.5h, performing gas phase analysis on the newly collected product. The results show that at the reaction temperature of 120 ℃, the hydrogen-hydrocarbon ratio of 1.0 and the liquid space velocity of cyclopentadiene of 9h-1Under the conditions, the conversion rate of cyclopentadiene was 96.7%, and the selectivity of cyclopentene was 93.3%.
Example 8:
12g of activated carbon was placed in 40mL of benzene and shaken ultrasonically at 0.5MHZ for 10 min. Under the condition of stirring, 3.6mL of trimethylchlorosilane is slowly dripped into the liquid, and the dripping speed is 0.6 mL/min. The liquid is placed in an ultrasonic cleaner and is subjected to ultrasonic oscillation for 3 hours at 2.4 MHZ. The liquid is filtered by suction, and the solid is washed by absolute ethyl alcohol and then is vacuumized and dried for 5 hours at the temperature of 130 ℃. 13mL of a nickel nitrate aqueous solution having a nickel concentration of 0.149g/mL was prepared. 10g of dried activated carbon is put into a nickel salt solution and immersed for 4 hours under equal volume stirring at room temperature. The solid was dried at 120 ℃ for 4 h. 13mL of an aqueous ruthenium chloride solution having a ruthenium concentration of 0.013g/mL was prepared. Putting the activated carbon loaded with nickel into a ruthenium chloride aqueous solution, and soaking for 4h at room temperature under equal volume stirring. Drying the solid at 120 ℃ for 4h, calcining the solid at 500 ℃ for 5h in a nitrogen atmosphere, and finally pre-reducing the solid at 500 ℃ for 5h in a hydrogen atmosphere to obtain the ruthenium modified activated carbon supported nickel catalyst with 16% of nickel load and 1.4% of ruthenium load.
Filling 5mL of the prepared catalyst into a reaction tube, introducing hydrogen at a hydrogen flow rate of 9.49L/h, opening a high-temperature circulator to circularly heat conduction oil to 113 ℃, then starting pumping cyclopentadiene for reaction, wherein the cyclopentadiene flow rate is 35mL/h (28g/h), adjusting the heat conduction oil flow rate and the heat exchange rate to maintain the reaction temperature at 120 ℃, then emptying a gas-liquid separation tank, collecting the product again, and after stable reaction for 0.5h, performing gas phase analysis on the newly collected product. The results show that at the reaction temperature of 120 ℃, the hydrogen-hydrocarbon ratio of 1.0 and the liquid space velocity of cyclopentadiene of 7h-1Under the conditions, the conversion rate of cyclopentadiene was 100%, and the selectivity of cyclopentene was 95.7%.

Claims (8)

1. A ruthenium modified activated carbon supported nickel catalyst for preparing cyclopentene by gas-phase selective hydrogenation of cyclopentadiene is characterized in that: the loading capacity of nickel is 16-20wt%, the loading capacity of ruthenium is 0.5-1.5wt%, and the balance is active carbon;
the preparation method of the catalyst comprises the following steps in sequence:
(1) putting activated carbon in a solvent, and carrying out ultrasonic oscillation;
(2) slowly dropwise adding a silylation reagent into the material obtained in the step (1) under the stirring condition;
(3) performing ultrasonic oscillation on the material obtained in the step (2) at high frequency;
(4) carrying out suction filtration on the material obtained in the step (3), washing the obtained solid with alcohol, and drying under a vacuum condition;
(5) preparing a nickel salt aqueous solution;
(6) putting the material obtained in the step (4) into the nickel salt solution obtained in the step (5), and stirring and dipping the material at the room temperature in the same volume;
(7) drying the solid in the material obtained in the step (6);
(8) preparing a ruthenium chloride aqueous solution;
(9) putting the material obtained in the step (7) into the ruthenium chloride aqueous solution obtained in the step (8), and stirring and dipping the material in the same volume at room temperature;
(10) and (4) drying, calcining and pre-reducing the solid in the material obtained in the step (9) to obtain the ruthenium modified activated carbon supported nickel catalyst.
2. The catalyst of claim 1, wherein: in the step (1), the solvent is benzene, diethyl ether or perchloroethylene, and the dosage of the active carbon relative to the solvent is 0.15-0.35 g/mL.
3. The catalyst of claim 1 or 2, wherein: in the step (2), the silylation reagent is at least one of trimethylchlorosilane, triethylchlorosilane or trimethoxychlorosilane, the volume-to-mass ratio of the silylation reagent to the activated carbon is 0.1-0.5mL/g, and the dropping rate of the silylation reagent is 0.3-1 mL/min.
4. The catalyst of claim 1 or 2, wherein: in the step (3), the ultrasonic oscillation time under high frequency is 1.5-4h, and the frequency is 1.7-2.4 MHZ; in the step (4), the alcohol washing reagent is absolute methanol or absolute ethanol; the drying temperature is 100-150 ℃, and the drying time is 4-10 h.
5. The catalyst of claim 1 or 2, wherein: in the step (5), the nickel salt is nickel nitrate, nickel acetate or nickel chloride, and the concentration of nickel in the nickel salt is 0.086-0.196 g/mL; the dipping time of the step (6) and the step (9) is 3-6 h.
6. The catalyst of claim 1 or 2, wherein: in the step (8), the concentration of ruthenium is 0.004-0.015 g/mL.
7. The catalyst of claim 1 or 2, wherein: in the step (10), the drying temperature is 100-150 ℃, and the time is 3-6 h; the calcining atmosphere is nitrogen or argon, the temperature is 400-; the pre-reduction adopts hydrogen as reducing gas, the reduction temperature is 400 ℃ and 500 ℃, and the reduction time is 4-8 h.
8. The method for applying the activated carbon-supported nickel catalyst according to claim 1, characterized in that: when the catalyst is applied to cyclopentadiene gas phase selective hydrogenation for preparing cyclopentene, the reaction temperature is 90-130 ℃, the hydrogen-hydrocarbon ratio is 0.8-1.2, and the liquid space velocity of cyclopentadiene is 4-9h -1。
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