CN113070078A - Rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst and preparation method thereof - Google Patents

Rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst and preparation method thereof Download PDF

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CN113070078A
CN113070078A CN202110274321.0A CN202110274321A CN113070078A CN 113070078 A CN113070078 A CN 113070078A CN 202110274321 A CN202110274321 A CN 202110274321A CN 113070078 A CN113070078 A CN 113070078A
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rare earth
catalyst
hydrogen storage
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storage medium
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CN113070078B (en
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梁鑫
张傑
赵宏
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Qingdao Chuangqixinneng Catalysis Technology Co ltd
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/04—Sulfides
    • C07C2527/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • C07C2527/051—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C07C2529/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Abstract

The invention discloses a rare earth element doped organic hydrogen storage medium hydrogenation monatomic catalyst, which comprises a carrier and an active component; the active component comprises three components of Co, Mo and S, and the carrier is a metal oxide doped with rare earth elements; the active component is dispersed and loaded on the carrier in a monoatomic form; the carrier is Al doped with rare earth elements with the total content not more than 5 wt%2O3The rare earth element is one or more rare earth metals selected from Ce, La and Y; the loading amount of the active component on the carrier is 1-5 wt% calculated by the mass ratio of the active component to the carrier. The invention realizes the pair by doping rare earth metalThe modification of the carrier effectively improves the activity of the monatomic catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium, so that the hydrogenation of the organic hydrogen storage medium can be realized at lower temperature and pressure.

Description

Rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst and preparation method thereof
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to a rare earth element-doped hydrogenation monatomic catalyst of an organic hydrogen storage medium and a preparation method thereof.
Background
With the development of new energy technology, hydrogen energy becomes one of important energy carriers in the future human society by virtue of the advantages of high heat value, environmental friendliness, abundant resources and the like. In recent years, the hydrogen energy industry is continuously developed, and hydrogen production end equipment and hydrogen end technology are gradually developed and perfected, but the hydrogen long-distance storage and transportation technology for connecting the hydrogen production end equipment and the hydrogen production end equipment has not realized breakthrough. At present, the mainstream hydrogen transportation method is still high-pressure gaseous hydrogen storage and liquid hydrogen storage, and various novel hydrogen storage materials such as hydrogen storage alloy, carbon-based porous material, coordination oxide, liquid organic matter and the like are continuously improved, so that the novel hydrogen storage technology with higher efficiency and safety has wider prospect along with the wide application of hydrogen energy, especially in order to meet the flexible application in various scenes.
In recent years, the research on hydrogenation catalysts for liquid organic hydrogen storage is mainly carried out on noble metal catalysts, and although noble metals have good catalytic activity, the problem of higher cost is also caused by the large-scale use of noble metals, so that certain difficulty is caused for the large-scale popularization of the liquid organic hydrogen storage technology. Although some rare earth element doped hydrogenation catalysts exist in the prior art, the rare earth element doped hydrogenation catalysts are rarely applied in the specific field of liquid organic hydrogen storage, and the existing rare earth element doped hydrogenation catalysts also have the problems of low activity, hydrogenation under the conditions of higher temperature and pressure and the like.
Disclosure of Invention
Based on the technical problems, the invention provides a rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst and a preparation method thereof.
The technical solution adopted by the invention is as follows:
a rare earth element doped organic hydrogen storage medium hydrogenation monatomic catalyst comprises a carrier and an active component; the active component comprises three components of Co, Mo and S, and the carrier is a metal oxide doped with rare earth elements; the active component is dispersed and loaded on the carrier in a monoatomic form.
Preferably, the support is Al doped with a total content of rare earth elements not exceeding 5 wt%2O3The rare earth element is one or more rare earth metals selected from Ce, La and Y.
Preferably, the loading amount of the active component on the carrier is 1-5 wt% calculated by the mass ratio of the active component to the carrier.
A preparation method of rare earth element doped organic hydrogen storage medium hydrogenation monatomic catalyst comprises the following steps:
(1) mixing rare earth metal salt and Al (NO)3)3·9H2Dissolving O in deionized water in sequence, adding polyethylene glycol 400 as a dispersing agent, and uniformly stirring to obtain a mixed solution; dropwise adding ammonia water into the mixed solution under the stirring state, adjusting the pH value of the mixed solution to 8-10, and continuously stirring for reaction;
filtering under reduced pressure after the reaction is finished, washing the separated precipitate with deionized water, crystallizing in a constant-temperature water bath, performing suction filtration again after the crystallization is finished, then washing with absolute ethyl alcohol, and then drying in an oven to obtain a catalyst carrier precursor;
grinding the obtained catalyst carrier precursor, roasting in a muffle furnace, and obtaining Al doped with rare earth elements after roasting2O3A carrier;
(2) mixing Co (NO)3)2·6H2O and (NH)4)2MoO4Preparing a first impregnation liquid, adding the carrier prepared in the step (1) into the first impregnation liquid, standing, drying, and roasting in a muffle furnace to obtain a rare earth catalyst loaded with Co and Mo;
(3) will be (NH)4)2S2O3Dissolving the rare earth catalyst into water to prepare second impregnation liquid, adding the rare earth catalyst loaded with Co and Mo prepared in the step (2) into the second impregnation liquid, standing, and then drying to obtain a pre-vulcanized rare earth catalyst;
then using a rotary tube furnace to activate the pre-vulcanized rare earth catalyst at the temperature of 300-350 ℃ and H2Atmosphere under the pressure of 0.25-0.4MPa,and activating for 50-80 min to obtain the rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst.
Preferably, in step (1): rare earth metal salt and Al (NO)3)3·9H2The molar ratio of O is 1: 50-1: 20; the rare earth metal salt is selected from one or more of cerium nitrate, lanthanum nitrate and yttrium nitrate.
Preferably, in step (1): the mass fraction of the ammonia water is 3-6 wt%; the temperature of the constant-temperature water bath during crystallization is 90 ℃, and the crystallization time is 4 hours; the temperature of the oven is 90-120 ℃, and the drying time is 8-15 h; the roasting temperature in a muffle furnace is 500-570 ℃, and the roasting time is 3-6 h.
Preferably, in step (2): the mass percentage concentration of the first impregnation liquid is 1-6 wt%; the first impregnation liquid and Al doped with rare earth elements2O3The volume ratio of the carriers is 1-1.5: 0.5-1; co (NO)3)2·6H2O and (NH)4)2MoO4The mass ratio of (A) to (B) is 0.5-1: 0.1-1.
Preferably, in step (2): standing for 15-20 h; the drying temperature is 90-120 ℃, and the drying time is 8-15 h; the roasting temperature in a muffle furnace is 500-570 ℃, and the roasting time is 3-6 h.
Preferably, in step (3): the concentration of the second impregnation liquid is 0.5-1 mol/L; the dosage of the second impregnation liquid is as follows: taking a second impregnation liquid according to the proportion of 1-3 mL of the second impregnation liquid per g of the rare earth catalyst loaded with Co and Mo; standing for 5 h; the drying temperature is 90-120 ℃, and the drying time is 8-15 h.
The rare earth element doped organic hydrogen storage medium hydrogenation monatomic catalyst can be used for hydrogenation reaction in an organic liquid hydrogen storage medium and can also be used for hydrogenation heterogeneous catalytic reaction in the chemical industry.
Taking the application in the hydrogenation of the organic hydrogen storage medium as an example, the organic hydrogen storage medium and the catalyst are mixed according to the mass ratio of 6: 1-25: 1, then the mixture is added into a dynamic reaction kettle, magnetons are added simultaneously, and then nitrogen is continuously introduced to replace the air existing in the dynamic reaction kettle. And after 5min, introducing hydrogen to replace the nitrogen, replacing for 10min, closing a gas outlet, adjusting the pressure of the hydrogen to 7-10MPa, raising the temperature to 150-230 ℃, and reacting for 1-8 h. The mixture was cooled to room temperature, at which point the introduction of hydrogen was stopped and replaced with nitrogen. After the replacement is finished, the residual liquid in the reaction kettle can be taken out and detected by using gas phase/liquid phase chromatography, and the hydrogen storage amount of the hydrogen storage medium can be converted according to the variety and the proportion of each product.
The organic hydrogen storage medium is selected from one of benzene, toluene, naphthalene, carbazole, methylcarbazole and dibenzyltoluene.
The beneficial technical effects of the invention are as follows:
(1) according to the invention, the modification of the carrier is realized by doping the rare earth metal, so that the activity of the monatomic catalyst for catalyzing the hydrogenation reaction of the organic hydrogen storage medium is effectively improved, the organic hydrogen storage medium can be hydrogenated at lower temperature and pressure, and the storage of hydrogen is realized. Specifically, the hydrogenation reaction can be carried out at a temperature of 150-230 ℃ and a hydrogen pressure of 7-10 Mpa.
(2) The invention combines the reduction activation and the like by using a rotary tube furnace on the basis of modifying the carrier by using rare earth metal doping, realizes the monoatomic dispersion of the load metal, greatly improves the utilization rate of active ingredients, and improves the conversion rate and the selectivity.
(3) When the catalyst prepared by the invention is applied to hydrogenation of a liquid organic hydrogen storage medium, the catalyst has higher conversion rate and selectivity, can saturate the hydrogen storage medium to a greater extent, and can be more fully applied to the hydrogen storage capacity of the hydrogen storage medium; in the hydrogenation reaction of the organic hydrogen storage medium, the highest conversion rate of the catalyst to toluene can reach 90 percent, wherein the selectivity of the methylcyclohexane can reach more than 95 percent.
(4) The catalyst is prepared by doping rare earth metal, so that compared with a noble metal catalyst, the cost of the catalyst is reduced, and the large-scale popularization of the liquid organic hydrogen storage technology is facilitated.
Drawings
FIG. 1 is activity evaluation data of a catalyst prepared by changing rare earth metal elements doped in a carrier synthesized by the method of the present invention;
FIG. 2 is activity evaluation data of a catalyst synthesized by the method of the present invention and prepared by changing the amount of an active component supported by a carrier;
FIG. 3 is activity evaluation data of catalysts prepared by the method of the present invention and comparative example.
Detailed Description
The invention provides a rare earth element doped organic hydrogen storage medium hydrogenation monatomic catalyst, which comprises a carrier and an active component; the active component comprises three components of Co, Mo and S, and the carrier is a metal oxide doped with rare earth elements; the active component is dispersed and loaded on the carrier in a monoatomic form.
The carrier is Al doped with rare earth elements with the total content not more than 5 wt%2O3The rare earth element is one or more rare earth metals selected from Ce, La and Y.
The loading amount of the active component on the carrier is 1-5 wt% calculated by the mass ratio of the active component to the carrier. Within the above-mentioned loading range, the active component can be dispersed on the carrier in the form of a single atom.
The invention is further illustrated by the following specific examples.
Example 1
18.75g of Al (NO) are weighed out3)3·9H2O and 0.868g Ce (NO)3)3·6H2Dissolving O in 500mL of deionized water, stirring at the normal temperature at the speed of 300r/min for 10min, adding 2mL of polyethylene glycol 400 serving as a dispersing agent, and continuously stirring for 15min to obtain a mixed solution. And meanwhile, preparing ammonia water with the mass fraction of 5 wt%, dropwise adding the ammonia water into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reaction for 40min, and then closing stirring. And (3) separating out the precipitate by vacuum filtration, washing the obtained precipitate for 3 times by using deionized water, then putting the precipitate into a water bath with the constant temperature of 90 ℃ for crystallization for 4 hours, washing the precipitate for 3 times by using absolute ethyl alcohol after the crystallization is finished, and then putting the precipitate into a drying oven with the temperature of 100 ℃ for drying for 10 hours to obtain the catalyst carrier precursor. Grinding the catalyst carrier precursor into powder and placing the powder into a muffle furnace 5Roasting at 50 ℃ for 6h to obtain Al doped with rare earth metal Ce2O3And (3) a carrier.
0.218g Co (NO) was weighed out3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared Al doped with rare earth metal Ce into the immersion liquid2O3Standing the carrier at room temperature overnight, drying at 100 ℃ for 10h, and roasting in a muffle furnace at 550 ℃ for 3h to obtain Co and Mo loaded CoMo/Ce-Al2O3A catalyst.
Taking the prepared CoMo/Ce-Al2O34g of catalyst, 10mL of 0.5mol/L (NH)4)2S2O3Standing the impregnation liquid at room temperature for 4h, and drying at 90 ℃ for 4h to obtain the pre-vulcanized catalyst. Putting the mixture into a rotary tube furnace to be activated in a hydrogen atmosphere at the activation temperature of 300 ℃, the heating rate of 1 ℃/s, the rotating speed of 30r/min, the activation pressure of 0.25-0.4Mpa and the activation time of 60min to obtain the catalyst CoMoS/Ce-Al for the hydrogenation of the organic hydrogen storage medium2O3。
The catalyst is used for toluene hydrogenation, 1g of the catalyst and 10g of toluene are weighed and transferred into a high-pressure reaction kettle, the hydrogen pressure is adjusted to 10Mpa, and the reaction temperature is increased to 160 ℃. And stopping the reaction after 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, performing qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry), and performing experiments for 2-8 hours respectively according to the method to obtain the effect of the catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium.
Example 2
18.75g of Al (NO) are weighed out3)3·9H2O and 0.866g La (NO)3)3·6H2Dissolving O in 500mL of deionized water, stirring at the normal temperature at the speed of 300r/min for 10min, adding 2mL of polyethylene glycol 400 serving as a dispersing agent, and continuously stirring for 15min to obtain a mixed solution. And meanwhile, preparing ammonia water with the mass fraction of 5 wt%, dropwise adding the ammonia water into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reaction for 40min, and then closing stirring.And (3) separating out the precipitate by vacuum filtration, washing the obtained precipitate for 3 times by using deionized water, then putting the precipitate into a water bath with the constant temperature of 90 ℃ for crystallization for 4 hours, washing the precipitate for 3 times by using absolute ethyl alcohol after the crystallization is finished, and then putting the precipitate into a drying oven with the temperature of 100 ℃ for drying for 10 hours to obtain the catalyst carrier precursor. Grinding the precursor of the catalyst carrier into powder and putting the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃, thus obtaining the Al doped with the rare earth metal La2O3And (3) a carrier.
Weigh 0.218g Co (NO)3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL water to obtain a soaking solution, and adding 5g of the prepared Al doped with rare earth metal La into the soaking solution2O3The support was allowed to stand at room temperature overnight. Drying at 100 ℃ for 10h, and roasting in a muffle furnace at 550 ℃ for 3h to obtain the catalyst loaded with Co and Mo.
Taking the prepared CoMo/La-AL2O34g, 10mL of 0.5mol/L (NH)4)2S2O3Standing the impregnation liquid at room temperature for 4h, and drying at 90 ℃ for 4h to obtain the pre-vulcanized catalyst. Putting the mixture into a rotary tube furnace to be activated in a hydrogen atmosphere at the activation temperature of 300 ℃, the heating rate of 1 ℃/s, the rotating speed of 30r/min, the activation pressure of 0.25-0.4Mpa and the activation time of 60min to obtain the catalyst CoMoS/La-Al for the hydrogenation of the organic hydrogen storage medium2O3。
The catalyst is used for toluene hydrogenation, 1g of the catalyst and 10g of toluene are weighed and transferred into a high-pressure reaction kettle, the hydrogen pressure is adjusted to 10Mpa, and the reaction temperature is increased to 160 ℃. And stopping the reaction after 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, performing qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry), and performing experiments for 2-8 hours respectively according to the method to obtain the effect of the catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium.
Example 3
18.75g of Al (NO) are weighed out3)3·9H2O and 0.766g of Y (NO)3)3·6H2O is dissolved in 500mL of deionized water at room temperature of 30Stirring at 0r/min for 10min, adding 2mL polyethylene glycol 400 as dispersant, and stirring for 15min to obtain mixed solution. And meanwhile, preparing ammonia water with the mass fraction of 5 wt%, dropwise adding the ammonia water into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reaction for 40min, and then closing stirring. And (3) separating out the precipitate by vacuum filtration, washing the obtained precipitate for 3 times by using deionized water, then putting the precipitate into a water bath with the constant temperature of 90 ℃ for crystallization for 4 hours, washing the precipitate for 3 times by using absolute ethyl alcohol after the crystallization is finished, and then putting the precipitate into a drying oven with the temperature of 100 ℃ for drying for 10 hours to obtain the catalyst carrier precursor. Grinding the precursor of the catalyst carrier into powder and putting the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃, thus obtaining the Al doped with the rare earth metal Y2O3And (3) a carrier.
0.218g Co (NO) was weighed out3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL water to obtain a soaking solution, and adding 5g of the obtained Al doped with rare earth metal Y2O3The support was allowed to stand at room temperature overnight. Drying at 100 ℃ for 10h, and roasting in a muffle furnace at 550 ℃ for 3h to obtain the catalyst loaded with Co and Mo.
Taking the prepared CoMo/Y-AL2O34g, 10mL of 0.5mol/L (NH)4)2S2O3Standing the impregnation liquid at room temperature for 4h, and drying at 90 ℃ for 4h to obtain the pre-vulcanized catalyst. Putting the mixture into a rotary tube furnace to be activated in a hydrogen atmosphere at the activation temperature of 300 ℃, the heating rate of 1 ℃/s, the rotating speed of 30r/min, the activation pressure of 0.25-0.4Mpa and the activation time of 60min to obtain the catalyst CoMoS/Y-Al for the hydrogenation of the organic hydrogen storage medium2O3。
The catalyst is used for toluene hydrogenation, 1g of the catalyst and 10g of toluene are weighed and transferred into a high-pressure reaction kettle, the hydrogen pressure is adjusted to 10Mpa, and the reaction temperature is increased to 160 ℃. And stopping the reaction after 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, performing qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry), and performing experiments for 2-8 hours respectively according to the method to obtain the effect of the catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium.
Example 4
18.75g of Al (NO) are weighed out3)3·9H2O and 0.433g La (NO)3)3·6H2O and 0.434g Ce (NO)3)3·6H2Dissolving O in 500mL of deionized water, stirring at the normal temperature at the speed of 300r/min for 10min, adding 2mL of polyethylene glycol 400 serving as a dispersing agent, and continuously stirring for 15min to obtain a mixed solution. And meanwhile, preparing ammonia water with the mass fraction of 5 wt%, dropwise adding the ammonia water into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reaction for 40min, and then closing stirring. And (3) separating out the precipitate by vacuum filtration, washing the obtained precipitate for 3 times by using deionized water, then putting the precipitate into a water bath with the constant temperature of 90 ℃ for crystallization for 4 hours, washing the precipitate for 3 times by using absolute ethyl alcohol after the crystallization is finished, and then putting the precipitate into a drying oven with the temperature of 100 ℃ for drying for 10 hours to obtain the catalyst carrier precursor. Grinding the precursor of the catalyst carrier into powder and putting the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃, thus obtaining the Al doped with the rare earth metals Ce and La2O3And (3) a carrier.
Weigh 0.218g Co (NO)3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL water to obtain an immersion liquid, and adding 6g of the prepared Al doped with rare earth metals Ce and La into the immersion liquid2O3The support was allowed to stand at room temperature overnight. Drying at 100 ℃ for 10h, and roasting in a muffle furnace at 550 ℃ for 3h to obtain the catalyst loaded with Co and Mo.
Taking the prepared CoMo/Ce-La-AL2O34g, 10mL of 0.5mol/L (NH)4)2S2O3Standing the impregnation liquid at room temperature for 4h, and drying at 90 ℃ for 4h to obtain the pre-vulcanized catalyst. Putting the mixture into a rotary tube furnace to be activated in a hydrogen atmosphere at the activation temperature of 300 ℃, the heating rate of 1 ℃/s, the rotating speed of 30r/min, the activation pressure of 0.25-0.4Mpa and the activation time of 60min to obtain the catalyst CoMoS/Ce-La-Al for the hydrogenation of the organic hydrogen storage medium2O3。
The catalyst is used for toluene hydrogenation, 1g of the catalyst and 10g of toluene are weighed and transferred into a high-pressure reaction kettle, the hydrogen pressure is adjusted to 10Mpa, and the reaction temperature is increased to 160 ℃. And stopping the reaction after 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, performing qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry), and performing experiments for 2-8 hours respectively according to the method to obtain the effect of the catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium.
Example 5
18.75g of Al (NO) are weighed out3)3·9H2O and 0.383g of Y (NO)3)3·6H2O and 0.434g Ce (NO)3)3·6H2Dissolving O in 500mL of deionized water, stirring at the normal temperature at the speed of 300r/min for 10min, adding 2mL of polyethylene glycol 400 serving as a dispersing agent, and continuously stirring for 15min to obtain a mixed solution. And meanwhile, preparing ammonia water with the mass fraction of 5 wt%, dropwise adding the ammonia water into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reaction for 40min, and then closing stirring. And (3) separating out the precipitate by vacuum filtration, washing the obtained precipitate for 3 times by using deionized water, then putting the precipitate into a water bath with the constant temperature of 90 ℃ for crystallization for 4 hours, washing the precipitate for 3 times by using absolute ethyl alcohol after the crystallization is finished, and then putting the precipitate into a drying oven with the temperature of 100 ℃ for drying for 10 hours to obtain the catalyst carrier precursor. Grinding the precursor of the catalyst carrier into powder and putting the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃, thus obtaining the Al doped with the rare earth metals Ce and Y2O3And (3) a carrier.
Weigh 0.218g Co (NO)3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared Al doped with rare earth metals Ce and Y into the immersion liquid2O3And (3) standing the carrier at room temperature overnight, drying at 100 ℃ for 10h, and roasting in a muffle furnace at 550 ℃ for 3h to obtain the Co and Mo loaded catalyst.
Taking the prepared CoMo/Ce-Y-Al2O34g, 10mL of 0.5mol/L (NH)4)2S2O3Standing the impregnation liquid at room temperature for 4h, and drying at 90 ℃ for 4h to obtain the pre-vulcanized catalyst. Will be provided withThe catalyst is put into a rotary tube furnace to be activated in hydrogen atmosphere, the activation temperature is 300 ℃, the heating rate is 1 ℃/s, the rotating speed is 30r/min, the activation pressure is 0.25Mpa, and the activation time is 60min, so that the catalyst CoMoS/Ce-Y-Al for the hydrogenation of the organic hydrogen storage medium is obtained2O3。
The catalyst is used for toluene hydrogenation, 1g of the catalyst and 10g of toluene are weighed and transferred into a high-pressure reaction kettle, the hydrogen pressure is adjusted to 10Mpa, and the reaction temperature is increased to 160 ℃. And stopping the reaction after 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, performing qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry), and performing experiments for 2-8 hours respectively according to the method to obtain the effect of the catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium.
Example 6
18.75g of Al (NO) are weighed out3)3·9H2O and 0.383g of Y (NO)3)3·6H2O and 0.433g La (NO)3)3·6H2Dissolving O in 500mL of deionized water, stirring at the normal temperature at the speed of 300r/min for 10min, adding 2mL of polyethylene glycol 400 serving as a dispersing agent, and continuously stirring for 15min to obtain a mixed solution. And meanwhile, preparing ammonia water with the mass fraction of 5 wt%, dropwise adding the ammonia water into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reaction for 40min, and then closing stirring. And (3) separating out the precipitate by vacuum filtration, washing the obtained precipitate for 3 times by using deionized water, then putting the precipitate into a water bath with the constant temperature of 90 ℃ for crystallization for 4 hours, washing the precipitate for 3 times by using absolute ethyl alcohol after the crystallization is finished, and then putting the precipitate into a drying oven with the temperature of 100 ℃ for drying for 10 hours to obtain the catalyst carrier precursor. Grinding the precursor of the catalyst carrier into powder and putting the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃, thus obtaining the Al doped with the rare earth metals La and Y2O3And (3) a carrier.
Weigh 0.655gCo (NO)3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL water to obtain a soaking solution, and adding 4g of the prepared Al doped with rare earth metals La and Y into the soaking solution2O3The carrier was allowed to stand overnight at room temperature and dried at 100 deg.CDrying for 10h, and roasting in a muffle furnace at 550 ℃ for 3h to obtain the catalyst loaded with Co and Mo.
Taking the prepared CoMo/Y-La-Al2O35g, 10mL of 0.5mol/L (NH)4)2S2O3Standing the impregnation liquid at room temperature for 4h, and drying at 90 ℃ for 4h to obtain the pre-vulcanized catalyst. Putting the activated carbon into a rotary tube furnace to be activated in a hydrogen atmosphere at the activation temperature of 300 ℃, the heating rate of 1 ℃/s, the rotating speed of 30r/min, the activation pressure of 0.4Mpa and the activation time of 60min to obtain the catalyst CoMoS/Y-La-Al for the hydrogenation of the organic hydrogen storage medium2O3。
The catalyst is used for toluene hydrogenation, 1g of the catalyst and 10g of toluene are weighed and transferred into a high-pressure reaction kettle, the hydrogen pressure is adjusted to 10Mpa, and the reaction temperature is increased to 160 ℃. And stopping the reaction after 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, performing qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry), and performing experiments for 2-8 hours respectively according to the method to obtain the effect of the catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium.
Example 7
18.75g of Al (NO) are weighed out3)3·9H2O and 0.868g Ce (NO)3)3·6H2Dissolving O in 500mL of deionized water, stirring at the normal temperature at the speed of 300r/min for 10min, adding 2mL of polyethylene glycol 400 serving as a dispersing agent, and continuously stirring for 15min to obtain a mixed solution. And meanwhile, preparing ammonia water with the mass fraction of 5 wt%, dropwise adding the ammonia water into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reaction for 40min, and then closing stirring. And (3) separating out the precipitate by vacuum filtration, washing the obtained precipitate for 3 times by using deionized water, then putting the precipitate into a water bath with the constant temperature of 90 ℃ for crystallization for 4 hours, washing the precipitate for 3 times by using absolute ethyl alcohol after the crystallization is finished, and then putting the precipitate into a drying oven with the temperature of 100 ℃ for drying for 10 hours to obtain the catalyst carrier precursor. Grinding the precursor of the catalyst carrier into powder and putting the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃, thus obtaining the Al doped with the rare earth metal Ce2O3And (3) a carrier.
0.109g of Co was weighed(NO3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared Al doped with rare earth metal Ce into the immersion liquid2O3The support was allowed to stand at room temperature overnight. Drying at 100 ℃ for 10h, and roasting in a muffle furnace at 550 ℃ for 3h to obtain the catalyst loaded with Co and Mo.
Taking the prepared CoMo/Ce-Al2O34g, 10mL of 0.5mol/L (NH)4)2S2O3Standing the impregnation liquid at room temperature for 4h, and drying at 90 ℃ for 4h to obtain the pre-vulcanized catalyst. Putting the activated carbon into a rotary tube furnace to be activated in a hydrogen atmosphere at the activation temperature of 300 ℃, the heating rate of 1 ℃/s, the rotating speed of 30r/min, the activation pressure of 0.3Mpa and the activation time of 60min to obtain the catalyst CoMoS/Ce-Al for the hydrogenation of the organic hydrogen storage medium2O3。
The catalyst is used for toluene hydrogenation, 1g of the catalyst and 10g of toluene are weighed and transferred into a high-pressure reaction kettle, the hydrogen pressure is adjusted to 10Mpa, and the reaction temperature is increased to 160 ℃. And stopping the reaction after 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, performing qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry), and performing experiments for 2-8 hours respectively according to the method to obtain the effect of the catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium.
Example 8
18.75g of Al (NO) are weighed out3)3·9H2O and 0.868g Ce (NO)3)3·6H2Dissolving O in 500mL of deionized water, stirring at the normal temperature at the speed of 300r/min for 10min, adding 2mL of polyethylene glycol 400 serving as a dispersing agent, and continuously stirring for 15min to obtain a mixed solution. And meanwhile, preparing ammonia water with the mass fraction of 5 wt%, dropwise adding the ammonia water into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reaction for 40min, and then closing stirring. Vacuum filtering to separate out precipitate, washing the obtained precipitate with deionized water for 3 times, crystallizing in water bath at 90 deg.C for 4 hr, washing with anhydrous ethanol for 3 times, and adding 1And drying in an oven at 00 ℃ for 10 hours to obtain a catalyst carrier precursor. Grinding the precursor of the catalyst carrier into powder and putting the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃, thus obtaining the Al doped with the rare earth metal Ce2O3And (3) a carrier.
Weigh 0.436g Co (NO)3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared Al doped with rare earth metal Ce into the immersion liquid2O3And (3) standing the carrier at room temperature overnight, drying at 100 ℃ for 10h, and roasting in a muffle furnace at 550 ℃ for 3h to obtain the Co and Mo loaded catalyst.
Taking the prepared CoMo/Ce-Al2O34g, 10mL of 0.5mol/L (NH)4)2S2O3Standing the impregnation liquid at room temperature for 4h, and drying at 90 ℃ for 4h to obtain the pre-vulcanized catalyst. Putting the mixture into a rotary tube furnace to be activated in a hydrogen atmosphere at the activation temperature of 300 ℃, the heating rate of 1 ℃/s, the rotating speed of 30r/min, the activation pressure of 0.25-0.4Mpa and the activation time of 60min to obtain the catalyst CoMoS/Ce-Al for the hydrogenation of the organic hydrogen storage medium2O3。
The catalyst is used for toluene hydrogenation, 1g of the catalyst and 10g of toluene are weighed and transferred into a high-pressure reaction kettle, the hydrogen pressure is adjusted to 10Mpa, and the reaction temperature is increased to 160 ℃. And stopping the reaction after 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, performing qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry), and performing experiments for 2-8 hours respectively according to the method to obtain the effect of the catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium.
Fig. 1 is activity evaluation data of a catalyst prepared by changing rare earth metal elements doped in a carrier synthesized by the method of the present invention, and it can be found that several catalysts prepared by changing the types of rare earth metals can realize high-efficiency hydrogenation on an organic hydrogen storage medium.
Fig. 2 is activity evaluation data of the catalyst prepared by changing the dosage ratio of the active component supported by the carrier, which is synthesized by the method of the present invention, and it can be found that the two catalysts prepared by changing the dosage ratio of the supported active component have different effects, but can realize high-efficiency hydrogenation for the organic hydrogen storage medium.
The effects of the present invention are further illustrated by several sets of comparative examples.
Comparative example 1
18.75g of Al (NO) are weighed out3)3·9H2Dissolving O in 500mL of deionized water, stirring at the normal temperature at the speed of 300r/min for 10min, adding 2mL of polyethylene glycol 400 serving as a dispersing agent, and continuously stirring for 15min to obtain a mixed solution. And meanwhile, preparing ammonia water with the mass fraction of 5 wt%, dropwise adding the ammonia water into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reaction for 40min, and then closing stirring. And (3) separating out the precipitate by vacuum filtration, washing the obtained precipitate for 3 times by using deionized water, then putting the precipitate into a water bath with the constant temperature of 90 ℃ for crystallization for 4 hours, washing the precipitate for 3 times by using absolute ethyl alcohol after the crystallization is finished, and then putting the precipitate into a drying oven with the temperature of 100 ℃ for drying for 10 hours to obtain the catalyst carrier precursor. Grinding the precursor of the catalyst carrier into powder and putting the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃, thus obtaining Al2O3And (3) a carrier.
Weigh 0.218g Co (NO)3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared Al into the immersion liquid2O3And (3) standing the carrier at room temperature overnight, drying at 100 ℃ for 10h, and roasting in a muffle furnace at 550 ℃ for 3h to obtain the Co and Mo loaded catalyst.
Taking the prepared CoMo/Al2O34g, 10mL of 0.5mol/L (NH)4)2S2O3Standing the impregnation liquid at room temperature for 4h, and drying at 90 ℃ for 4h to obtain the pre-vulcanized catalyst. Putting the mixture into a rotary tube furnace to be activated in a hydrogen atmosphere at the activation temperature of 300 ℃, the heating rate of 1 ℃/s, the rotating speed of 30r/min, the activation pressure of 0.25-0.4Mpa and the activation time of 60min to obtain the catalyst CoMoS/Al for the hydrogenation of the organic hydrogen storage medium2O3。
The catalyst is used for toluene hydrogenation, 1g of the catalyst and 10g of toluene are weighed and transferred into a high-pressure reaction kettle, the hydrogen pressure is adjusted to 10Mpa, and the reaction temperature is increased to 160 ℃. And stopping the reaction after 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, performing qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry), and performing experiments for 2-8 hours respectively according to the method to obtain the effect of the catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium.
Comparative example 2
18.75g of Al (NO) are weighed out3)3·9H2O and 0.868g Ce (NO)3)3·6H2Dissolving O in 500mL of deionized water, stirring at the normal temperature at the speed of 300r/min for 10min, adding 2mL of polyethylene glycol 400 serving as a dispersing agent, and continuously stirring for 15min to obtain a mixed solution. And meanwhile, preparing ammonia water with the mass fraction of 5 wt%, dropwise adding the ammonia water into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reaction for 40min, and then closing stirring. And (3) separating out the precipitate by vacuum filtration, washing the obtained precipitate for 3 times by using deionized water, then putting the precipitate into a water bath with the constant temperature of 90 ℃ for crystallization for 4 hours, washing the precipitate for 3 times by using absolute ethyl alcohol after the crystallization is finished, and then putting the precipitate into a drying oven with the temperature of 100 ℃ for drying for 10 hours to obtain the catalyst carrier precursor. Grinding the precursor of the catalyst carrier into powder and putting the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃, thus obtaining Al2O3And (3) a carrier.
0.218g Co (NO) was weighed out3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared Al into the immersion liquid2O3And (3) standing the carrier at room temperature overnight, drying at 100 ℃ for 10h, and roasting in a muffle furnace at 550 ℃ for 3h to obtain the Co and Mo loaded catalyst.
4g of catalyst is put into a rotary tube furnace to be activated in hydrogen atmosphere at the activation temperature of 300 ℃, the heating rate of 1 ℃/s, the rotating speed of 30r/min, the activation pressure of 0.25-0.4Mpa and the activation time of 60min, and the catalyst CoMo/Al which is not vulcanized and is used for hydrogenation of the organic hydrogen storage medium is obtained2O3。
The catalyst is used for toluene hydrogenation, 1g of the catalyst and 10g of toluene are weighed and transferred into a high-pressure reaction kettle, the hydrogen pressure is adjusted to 10Mpa, and the reaction temperature is increased to 160 ℃. And stopping the reaction after 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, performing qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry), and performing experiments for 2-8 hours respectively according to the method to obtain the effect of the catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium.
Comparative example 3
18.75g of Al (NO) are weighed out3)3·9H2O and 0.868g Ce (NO)3)3·6H2Dissolving O in 500mL of deionized water, stirring at the normal temperature at the speed of 300r/min for 10min, adding 2mL of polyethylene glycol 400 serving as a dispersing agent, and continuously stirring for 15min to obtain a mixed solution. And meanwhile, preparing ammonia water with the mass fraction of 5 wt%, dropwise adding the ammonia water into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reaction for 40min, and then closing stirring. And (3) separating out the precipitate by vacuum filtration, washing the obtained precipitate for 3 times by using deionized water, then putting the precipitate into a water bath with the constant temperature of 90 ℃ for crystallization for 4 hours, washing the precipitate for 3 times by using absolute ethyl alcohol after the crystallization is finished, and then putting the precipitate into a drying oven with the temperature of 100 ℃ for drying for 10 hours to obtain the catalyst carrier precursor. Grinding the precursor of the catalyst carrier into powder and putting the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃, thus obtaining Al2O3And (3) a carrier.
Weigh 0.218g Co (NO)3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared Al into the immersion liquid2O3And (3) standing the carrier at room temperature overnight, drying at 100 ℃ for 10h, and roasting in a muffle furnace at 550 ℃ for 3h to obtain the Co and Mo loaded catalyst.
Taking the prepared CoMo/Al2O34g, 10mL of 0.5mol/L (NH)4)2S2O3Standing the impregnation liquid at room temperature for 4h, and drying at 90 ℃ for 4h to obtain the pre-vulcanized catalyst. Putting it into a common tube furnace to be activated in hydrogen atmosphereThe activation temperature is 300 ℃, the heating rate is 1 ℃/s, the activation pressure is 0.25-0.4Mpa, the activation time is 60min, and the catalyst CoMoS/Al for the hydrogenation of the organic hydrogen storage medium is obtained2O3。
The catalyst is used for toluene hydrogenation, 1g of the catalyst and 10g of toluene are weighed and transferred into a high-pressure reaction kettle, the hydrogen pressure is adjusted to 10Mpa, and the reaction temperature is increased to 160 ℃. And stopping the reaction after 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, performing qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry), and performing experiments for 2-8 hours respectively according to the method to obtain the effect of the catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium.
Fig. 3 is the activity evaluation data of the catalysts prepared in the method of the present invention and the comparative example, and it can be found that the hydrogenation activity of the catalyst prepared in the comparative example is significantly reduced compared to the catalyst prepared in the example.
Table 1 shows the comparison of the activity and selectivity of the catalysts prepared in different examples and comparative examples for catalyzing the hydrogenation reaction of toluene, and it can be found that the doping of rare earth metals into the carrier, the presulfurization, and the activation and reduction using the rotary tube furnace can improve the activity and selectivity of the catalyst in the hydrogenation reaction to different degrees.
TABLE 1
Detailed description of the preferred embodiments Catalyst and process for preparing same Conversion of toluene Methylcyclohexane selectivity
Example 1 Co1.5Mo3.5S/Ce-Al2O3 88 91
Example 2 Co1.5Mo3.5S/La-Al2O3 88 91
Example 3 Co1.5Mo3.5S/Y-Al2O3 87 94
Example 4 Co1.5Mo3.5S/Ce-La-Al2O3 90 92
Example 5 Co1.5Mo3.5S/Ce-Y-Al2O3 82 92
Example 6 Co1.5Mo3.5S/La-Y-Al2O3 89 92
Example 7 Co0.7Mo3.5S/Ce-Al2O3 81 95
Example 8 Co3Mo3.5S/Ce-Al2O3 86 93
Comparative example 1 Co1.5Mo3.5S/Al2O3 72 92
Comparative example 2 Co1.5Mo3.5/Ce-Al2O3Without being vulcanized 65 79
Comparative example 3 Co1.5Mo3.5S/Ce-Al2O3Using a common tube furnace 77 81

Claims (10)

1. A rare earth element doped organic hydrogen storage medium hydrogenation monatomic catalyst is characterized in that: the catalyst comprises a carrier and an active component; the active component comprises three components of Co, Mo and S, and the carrier is a metal oxide doped with rare earth elements; the active component is dispersed and loaded on the carrier in a monoatomic form.
2. The rare earth element doped organic hydrogen storage medium hydrogenation monatomic catalyst of claim 1, wherein: the carrier is Al doped with rare earth elements with the total content not more than 5 wt%2O3The rare earth element is one or more rare earth metals selected from Ce, La and Y.
3. The rare earth element doped organic hydrogen storage medium hydrogenation monatomic catalyst of claim 1, wherein: the loading amount of the active component on the carrier is 1-5 wt% calculated by the mass ratio of the active component to the carrier.
4. The method for preparing the rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst according to any one of claims 1 to 3, characterized by comprising the following steps:
(1) mixing rare earth metal salt and Al (NO)3)3·9H2Dissolving O in deionized water in sequence, adding polyethylene glycol 400 as a dispersing agent, and uniformly stirring to obtain a mixed solution; dropwise adding ammonia water into the mixed solution under the stirring state, adjusting the pH value of the mixed solution to 8-10, and continuously stirring for reaction;
filtering under reduced pressure after the reaction is finished, washing the separated precipitate with deionized water, crystallizing in a constant-temperature water bath, performing suction filtration again after the crystallization is finished, then washing with absolute ethyl alcohol, and then drying in an oven to obtain a catalyst carrier precursor;
grinding the obtained catalyst carrier precursor, roasting in a muffle furnace, and obtaining Al doped with rare earth elements after roasting2O3A carrier;
(2) mixing Co (NO)3)2·6H2O and (NH)4)2MoO4Preparing a first impregnation liquid, adding the carrier prepared in the step (1) into the first impregnation liquid, standing, drying, and roasting in a muffle furnace to obtain a rare earth catalyst loaded with Co and Mo;
(3) will be (NH)4)2S2O3Dissolving the rare earth catalyst into water to prepare second impregnation liquid, adding the rare earth catalyst loaded with Co and Mo prepared in the step (2) into the second impregnation liquid, standing, and then drying to obtain a pre-vulcanized rare earth catalyst;
then using a rotary tube furnace to activate the pre-vulcanized rare earth catalyst at the temperature of 300-350 ℃ and H2And (3) activating for 50-80 min under the pressure of 0.25-0.4Mpa to obtain the rare earth element doped organic hydrogen storage medium hydrogenation monatomic catalyst.
5. The method for preparing rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst according to claim 4, wherein in the step (1): rare earth metal salt and Al (NO)3)3·9H2The molar ratio of O is 1: 50-1: 20; the rare earth metal salt is selected from one or more of cerium nitrate, lanthanum nitrate and yttrium nitrate.
6. The method for preparing rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst according to claim 4, wherein in the step (1): the mass fraction of the ammonia water is 3-6 wt%; the temperature of the constant-temperature water bath during crystallization is 90 ℃, and the crystallization time is 4 hours; the temperature of the oven is 90-120 ℃, and the drying time is 8-15 h; the roasting temperature in a muffle furnace is 500-570 ℃, and the roasting time is 3-6 h.
7. The method for preparing rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst according to claim 4, wherein in the step (2): the mass percentage concentration of the first impregnation liquid is 1-6 wt%; the first impregnation liquid and Al doped with rare earth elements2O3The volume ratio of the carriers is 1-1.5: 0.5-1; co (NO)3)2·6H2O and (NH)4)2MoO4The mass ratio of (A) to (B) is 0.5-1: 0.1-1.
8. The method for preparing rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst according to claim 4, wherein in the step (2): standing for 15-20 h; the drying temperature is 90-120 ℃, and the drying time is 8-15 h; the roasting temperature in a muffle furnace is 500-570 ℃, and the roasting time is 3-6 h.
9. The method for preparing rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst according to claim 4, wherein in the step (3): the concentration of the second impregnation liquid is 0.5-1 mol/L; the dosage of the second impregnation liquid is as follows: taking a second impregnation liquid according to the proportion of 1-3 mL of the second impregnation liquid per g of the rare earth catalyst loaded with Co and Mo; standing for 5 h; the drying temperature is 90-120 ℃, and the drying time is 8-15 h.
10. The rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst as defined in any one of claims 1 to 3, which can be used for hydrogenation reactions in organic liquid hydrogen storage media, and hydrogenation heterogeneous catalytic reactions in the chemical industry.
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