CN113070077A - Composite carrier single-atom catalyst for hydrogenation of organic hydrogen storage medium and preparation method thereof - Google Patents

Composite carrier single-atom catalyst for hydrogenation of organic hydrogen storage medium and preparation method thereof Download PDF

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CN113070077A
CN113070077A CN202110241597.9A CN202110241597A CN113070077A CN 113070077 A CN113070077 A CN 113070077A CN 202110241597 A CN202110241597 A CN 202110241597A CN 113070077 A CN113070077 A CN 113070077A
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CN113070077B (en
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张傑
赵宏
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Qingdao Chuangqixinneng Catalysis Technology Co ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • 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
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    • Y02E60/30—Hydrogen technology
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Abstract

The invention discloses a composite carrier monatomic catalyst for hydrogenation of an organic hydrogen storage medium and a preparation method thereof2O3And ZrO2、MgO、TiO2One or two of the components are compounded; the active component is dispersed on the composite carrier in a single atom form. The loading amount of the active component on the composite carrier is 1-5 wt% calculated by the mass ratio of the active component to the composite carrier. The preparation method of the catalyst comprises the steps of using the composite metal oxide as a carrier, synthesizing the catalyst capable of realizing hydrogenation of the hydrogen storage medium by changing the carrier and the loaded active component, and reducing the catalyst by using a rotary tube furnaceThe active ingredient is dispersed monoatomic in the carrier. The catalyst prepared by the invention can catalyze the organic medium hydrogen storage reaction at lower temperature and lower pressure, and can improve the overall energy efficiency of the liquid organic hydrogen storage system.

Description

Composite carrier single-atom catalyst for hydrogenation of organic hydrogen storage medium and preparation method thereof
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to a composite carrier monatomic catalyst for hydrogenation 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. The current 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.
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. The use of non-noble metal doping, disclosed in chinese patent application No. CN202010406445.5, although the cost of the catalyst is reduced to some extent, does not fundamentally solve the problem. Therefore, the development of a non-noble metal hydrogenation catalyst with high dispersibility becomes one of the keys for popularizing the liquid organic hydrogen storage technology.
Disclosure of Invention
Based on the technical problems, the invention provides a composite carrier monatomic catalyst for hydrogenation of an organic hydrogen storage medium and a preparation method thereof.
The technical solution adopted by the invention is as follows:
a composite carrier single-atom catalyst for hydrogenating organic hydrogen-storing medium is composed of composite carrier and active component containing Co, Mo and S, and the composite carrier is Al2O3And ZrO2、MgO、TiO2One or two of the components are compounded; the active component is dispersed on the composite carrier in a single atom form.
The loading amount of the active component on the composite carrier is calculated by the mass ratio of the active component to the composite carrier, and is preferably 1-5 wt%.
A preparation method of a composite carrier monatomic catalyst for hydrogenation of an organic hydrogen storage medium comprises the following steps:
(1) sequentially dissolving aluminum and one or two metal salts of magnesium, zirconium and titanium in deionized water to obtain a solution I, adding polyethylene glycol 400 serving as a dispersing agent into the solution I, and stirring to obtain a mixed solution; adding ammonia water into the mixed solution, adjusting the pH value to 8-10, and continuously stirring for reaction; after the reaction is finished, filtering out a solid under reduced pressure, washing with deionized water, then placing into a constant-temperature water bath for crystallization, performing suction filtration after the crystallization is finished, then washing with absolute ethyl alcohol, and placing into an oven for drying to obtain a catalyst carrier precursor;
grinding the catalyst carrier precursor, and roasting in a muffle furnace to obtain a composite carrier;
(2) mixing Co (NO)3)2·6H2O and (NH)4)2MoO4Preparing a first impregnation liquid, adding the composite carrier obtained in the step (1) into the first impregnation liquid, standing, drying the composite carrier, and roasting in a muffle furnace to obtain a catalyst loaded with Co and Mo;
(3) will be (NH)4)2S2O3Dissolving the catalyst into deionized water to prepare a second impregnation solution, adding the Co and Mo loaded catalyst prepared in the step (2) into the second impregnation solution, standing, and drying the catalyst to obtain a pre-vulcanized catalyst;
then using a rotary tube furnace to activate the presulfurized catalyst at the temperature of 300-350 ℃ and H2And (3) activating for 50-80 min under the condition of 0.25-0.4Mpa of atmosphere to obtain the composite carrier monatomic catalyst for hydrogenation of the organic hydrogen storage medium.
Preferably, in step (1): one or two of magnesium, zirconium and titanium are called as other metal ions, wherein the molar concentration ratio of aluminum to the other metal ions is (1-5) to 1.
Preferably, in step (1): the volume ratio of the addition amount of the polyethylene glycol 400 to the solution I is 4 mL/L; the mass fraction of the ammonia water is 3-6 wt%; controlling the stirring time before ammonia water is dripped to be 10-15 min, and controlling the stirring time after ammonia water is dripped to be 40-50 min; the washing times of the deionized water and the absolute ethyl alcohol are respectively 3-5 times.
Preferably, in step (1): the temperature of the constant-temperature water bath during crystallization is 85-100 ℃, and the crystallization time is 3-5 h; the temperature of the oven is 90-120 ℃, and the drying time is 10 hours; the roasting temperature is 550 ℃ and the roasting time is 6 hours.
Preferably, in step (2): the mass percentage concentration of the first impregnation liquid is 1-6 wt%; loading the composite carrier by using an isometric impregnation method, wherein the volume ratio of the first impregnation liquid to the composite carrier is 1-1.5: 0.5-1; co (NO) in first impregnation liquid3)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 12-20 h; the drying temperature is 90-120 ℃, and the drying time is 8-15 h; the roasting temperature 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: and taking the second impregnation liquid according to the proportion of 1-3 mL of the second impregnation liquid per g of the catalyst loaded with Co and Mo.
Preferably, in step (3): standing for 4-5 h; the drying temperature is 80-90 ℃, and the drying time is 5-6 h.
Preferably, the rotating speed of the rotary tube furnace is 30 r/min.
The metal salt is selected from one or more of magnesium sulfate, zirconium acetate and titanium sulfate.
The composite carrier monatomic catalyst can be used for dehydrogenation reaction in an organic liquid hydrogen storage system and can be used for heterogeneous catalytic dehydrogenation reaction in the chemical industry.
Taking the application in hydrogenation of an organic hydrogen storage medium as an example, specifically, mixing the organic hydrogen storage medium and a catalyst in a mass ratio of 6: 1-25: 1, adding the mixture into a dynamic reaction kettle, adding magnetons at the same time, continuously introducing nitrogen to replace the air existing in the dynamic reaction kettle, introducing hydrogen to replace the nitrogen after 5min, closing a gas outlet after 10min replacement, adjusting the pressure of the hydrogen to 8-12MPa, raising the temperature to 160-220 ℃, 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) the catalyst prepared by the invention does not contain noble metal, has lower cost and is beneficial to the large-scale popularization of the liquid organic hydrogen storage technology.
(2) The catalyst prepared by the invention has the advantages that the catalyst performance is improved on one hand, the physical performance of the catalyst is enhanced on the other hand, and the stability of the catalyst is favorably maintained.
(3) The invention uses the rotary tube furnace for reduction activation, realizes the monoatomic dispersion of the loaded metal, greatly improves the utilization rate of active ingredients, reduces the cost of the catalyst, and improves the conversion rate and the selectivity.
(4) The invention uses composite metal oxide as carrier, and synthesizes catalyst which can realize hydrogen storage medium hydrogenation by changing carrier and loaded active component; the catalyst prepared by the invention can catalyze the hydrogen storage reaction of the organic medium at lower temperature and lower pressure, realize the storage of hydrogen, improve the overall energy efficiency of a liquid organic matter hydrogen storage system, and improve the stability and safety of the system operation.
(5) When the catalyst prepared by the invention is applied to hydrogenation of the 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, and the selectivity of the methylcyclohexane can reach 91 percent.
Drawings
FIG. 1 is activity evaluation data for catalysts prepared from different composite supports synthesized by the method of the present invention;
FIG. 2 is activity evaluation data of a catalyst prepared by changing a metal element supported by a carrier according to the method of the present invention;
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 composite carrier monatomic catalyst for hydrogenation of an organic hydrogen storage medium, which consists of a composite carrier and active components, wherein the active components comprise Co, Mo and S, and the composite carrier is Al2O3And ZrO2、MgO、TiO2One or two of the components are compounded; the active component is dispersed and loaded on the composite carrier in a monoatomic form.
In the catalyst, the loading amount of the active component on the composite carrier is 1-5 wt% calculated by the mass ratio of the active component to the composite carrier. Within the above-mentioned loading amount range, the active component can be dispersed on the composite 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 3.46g of MgSO4·H2Dissolving 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. Dropwise adding ammonia water with the mass fraction of 5 wt% 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 precipitate with deionized water for 3 times, crystallizing in water bath at 90 deg.C for 4 hr,and washing the obtained product for 3 times by using absolute ethyl alcohol after crystallization is finished, and then drying the product in a 100 ℃ oven for 10 hours to obtain a catalyst carrier precursor. Grinding the precursor into powder and placing the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃ to obtain the composite carrier MgO-Al2O3。
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 composite carrier MgO-Al into the immersion liquid2O3Standing overnight at room temperature, drying at 100 deg.C for 10h, calcining in muffle furnace at 550 deg.C for 3h to obtain Co and Mo loaded CoMo/MgO-Al2O3A catalyst.
Taking the prepared CoMo/MgO-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/MgO-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 for 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), thus obtaining the proportion of a reactant and a product, and performing experiments for 2-8 hours respectively according to the method, thus obtaining 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 8.19g of Zr (CH)3COO)4Dissolving in 500mL deionized water, stirring at 300r/min for 10min at normal temperature, adding 2mL polyethylene glycol 400 as dispersant, and stirring for 15min to obtain a mixed solution. Stirring the mixtureDropwise adding ammonia water with the mass fraction of 5 wt% into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reacting 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 into powder and placing the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃ to obtain the composite carrier ZrO2-Al2O3。
0.218g Co (NO) was weighed out3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL of water to prepare an impregnation solution, and adding 5g of the prepared composite carrier ZrO into the impregnation solution2-Al2O3Standing overnight at room temperature, drying at 100 deg.C for 10h, calcining in muffle furnace at 550 deg.C for 3h to obtain Co and Mo loaded CoMo/ZrO2-Al2O3A catalyst.
Taking the prepared CoMo/ZrO2-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/ZrO for hydrogenation of the organic hydrogen storage medium2-Al2O3。
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 for 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), thus obtaining the proportion of a reactant and a product, and performing experiments for 2-8 hours respectively according to the method, thus obtaining 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 6g of TiSO4Dissolving in 500mL deionized water, stirring at 300r/min for 10min at normal temperature, adding 2mL polyethylene glycol 400 as dispersant, and stirring for 15min to obtain a mixed solution. Dropwise adding ammonia water with the mass fraction of 5 wt% 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 into powder and placing the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃ to obtain the composite carrier TiO2-Al2O3。
Weigh 0.218g Co (NO)3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL water to prepare a maceration extract, and adding 6g of the prepared composite carrier TiO2·Al2O3Standing overnight at room temperature, drying at 100 deg.C for 10h, calcining in muffle furnace at 550 deg.C for 3h to obtain Co and Mo loaded CoMo/TiO2-Al2O3A catalyst.
Taking the prepared CoMo/TiO2-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 hydrogen atmosphere at the activation temperature of 300 ℃, the rotation speed of 30r/min, the activation pressure of 0.25-0.4Mpa and the activation time of 60min to obtain the catalyst CoMoS/TiO for hydrogenating the organic hydrogen storage medium2-Al2O3。
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 for 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), thus obtaining the proportion of a reactant and a product, and performing experiments for 2-8 hours respectively according to the method, thus obtaining 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 4.1g of Zr (CH3COO)4And 1.73g of MgSO4·H2Dissolving 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. Dropwise adding ammonia water with the mass fraction of 5 wt% 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 into powder and placing the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃ to obtain the composite carrier ZrO2-MgO-Al2O3。
Weigh 0.218g Co (NO)3)26H2O and 0.343g (NH)4)2MoO4Adding into 10mL of water to prepare an impregnation solution, and adding 5g of the prepared composite carrier ZrO into the impregnation solution2-MgO-Al2O3Standing overnight at room temperature, drying at 100 deg.C for 10h, calcining in muffle furnace at 550 deg.C for 3h to obtain Co and Mo loaded CoMo/ZrO2-MgO-Al2O3A catalyst.
Taking the prepared CoMo/ZrO2-MgO-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 hydrogen atmosphere at the activation temperature of 300 ℃, the rotating speed of 30r/min and the activation time of 60min to obtain the catalyst CoMoS ^ based on the hydrogenation of the organic hydrogen storage mediumZrO2-MgO-Al2O3。
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 for 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), thus obtaining the proportion of a reactant and a product, and performing experiments for 2-8 hours respectively according to the method, thus obtaining 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 4.1g of Zr (CH3COO)4And 3g of TiSO4Dissolving in 500mL deionized water, stirring at 300r/min for 10min at normal temperature, adding 2mL polyethylene glycol 400 as dispersant, and stirring for 15min to obtain a mixed solution. Dropwise adding ammonia water with the mass fraction of 5 wt% 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 into powder and placing the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃ to obtain the composite carrier ZrO2-TiO2-Al2O3。
Weigh 0.218g Co (NO)3)2·6H2O and 0.343g (NH)4)2MoO4Adding into 10mL of water to prepare an impregnation solution, and adding 5g of the prepared composite carrier ZrO into the impregnation solution2-TiO2-Al2O3Standing overnight at room temperature, drying at 100 deg.C for 10h, calcining in muffle furnace at 550 deg.C for 3h to obtain Co and Mo loaded CoMo/ZrO2-TiO2-Al2O3A catalyst.
Taking the prepared CoMo/ZrO2-TiO2-Al2O34g, adding 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 rotation speed of 30r/min, the activation pressure of 0.25-0.4Mpa and the activation time of 60min to obtain the catalyst CoMoS/ZrO for hydrogenating the organic hydrogen storage medium2-TiO2-Al2O3。
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 for 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), thus obtaining the proportion of a reactant and a product, and performing experiments for 2-8 hours respectively according to the method, thus obtaining 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 1.73g MgSO4·H2O and 3g of TiSO4Dissolving in 500mL deionized water, stirring at 300r/min for 10min at normal temperature, adding 2mL polyethylene glycol 400 as dispersant, and stirring for 15min to obtain a mixed solution. Dropwise adding ammonia water with the mass fraction of 5 wt% 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 into powder and placing the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃ to obtain the composite carrier MgO-TiO2-Al2O3。
Weigh 0.655g 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 MgO-TiO2-Al2O3Standing overnight at room temperature, drying at 100 deg.C for 10h, calcining in muffle furnace at 550 deg.C for 3h to obtain Co and Mo loaded CoMo/MgO-TiO2-Al2O3A catalyst.
Taking the prepared CoMo/MgO-TiO2-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/MgO-TiO for hydrogenating the organic hydrogen storage medium2-Al2O3。
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 for 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), thus obtaining the proportion of a reactant and a product, and performing experiments for 2-8 hours respectively according to the method, thus obtaining 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 3.46g of MgSO4·H2Dissolving 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. Dropwise adding ammonia water with the mass fraction of 5 wt% 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 into powder and putting the powder into a muffle furnace to be roasted for 6 hours at 550 ℃,to obtain the composite carrier MgO-Al2O3。
Weigh 0.109g 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 composite carrier MgO-Al into the immersion liquid2O3Standing overnight at room temperature, drying at 100 deg.C for 10h, calcining in muffle furnace at 550 deg.C for 3h to obtain Co and Mo loaded CoMo/MgO-Al2O3A catalyst.
Taking the prepared CoMo/MgO-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 rotation speed of 30r/min, the activation pressure of 0.25-0.4Mpa and the activation time of 60min to obtain the catalyst CoMoS/MgO-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 for 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), thus obtaining the proportion of a reactant and a product, and performing experiments for 2-8 hours respectively according to the method, thus obtaining 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 3.46g of MgSO4·H2Dissolving 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. Dropwise adding ammonia water with the mass fraction of 5 wt% 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 precipitate with deionized water for 3 times, and addingAnd (3) crystallizing in a water bath at 90 ℃ for 4h, washing for 3 times by using absolute ethyl alcohol after crystallization is finished, and then drying in a drying oven at 100 ℃ for 10 hours to obtain a catalyst carrier precursor. Grinding the precursor into powder and placing the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃ to obtain the composite carrier MgO-Al2O3。
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 composite carrier MgO-Al into the immersion liquid2O3Standing overnight at room temperature, drying at 100 deg.C for 10h, calcining in muffle furnace at 550 deg.C for 3h to obtain Co and Mo loaded CoMo/MgO-Al2O3A catalyst.
Taking the prepared CoMo/MgO-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/MgO-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 for 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), thus obtaining the proportion of a reactant and a product, and performing experiments for 2-8 hours respectively according to the method, thus obtaining the effect of the catalyst in catalyzing the hydrogenation reaction of the organic hydrogen storage medium.
Fig. 1 is activity evaluation data of catalysts prepared from different composite carriers synthesized by the method of the present invention, and it can be found that several catalysts prepared by changing metal species can realize high-efficiency hydrogenation for organic hydrogen storage media.
Fig. 2 is activity evaluation data of a catalyst prepared by changing a metal element loaded on a carrier, which is synthesized by the method of the present invention, and it can be found that several catalysts prepared by changing the kind of the loaded metal can realize high-efficiency hydrogenation on an organic hydrogen storage medium.
The processing equipment or devices not shown in the above examples are conventional in the art.
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. Dropwise adding ammonia water with the mass fraction of 5 wt% 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 into powder and putting the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃ to obtain 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. Activating in a rotary tube furnace in hydrogen atmosphere at 300 deg.C, 1 deg.C/s of heating rate, 30r/min of rotation speed, 0.25-0.4Mpa of activation pressure, and 60min of activation time to obtain the final productCatalyst CoMoS/Al for hydrogenation in 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 for 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), thus obtaining the proportion of a reactant and a product, and performing experiments for 2-8 hours respectively according to the method, thus obtaining 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 3.46g of MgSO4·H2Dissolving 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. Dropwise adding ammonia water with the mass fraction of 5 wt% 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 into powder and placing the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃ to obtain the composite carrier MgO-Al2O3。
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 composite carrier MgO-Al into the immersion liquid2O3Standing overnight at room temperature, drying at 100 deg.C for 10h, calcining in muffle furnace at 550 deg.C for 3h to obtain Co and Mo loaded CoMo/MgO-Al2O3A catalyst.
4g of CoMo/MgO-Al was taken2O3The 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, and the rotating speed is30r/min, the activation pressure is 0.25-0.4Mpa, the activation time is 60min, and the catalyst CoMo/MgO-Al which is not vulcanized and is used for hydrogenating 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 for 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), thus obtaining the proportion of a reactant and a product, and performing experiments for 2-8 hours respectively according to the method, thus obtaining 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 3.46g of MgSO4·H2Dissolving 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. Dropwise adding ammonia water with the mass fraction of 5 wt% 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 into powder and placing the powder into a muffle furnace to be roasted for 6 hours at the temperature of 550 ℃ to obtain the composite carrier MgO-Al2O3。
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 composite carrier MgO-Al into the immersion liquid2O3Standing overnight at room temperature, drying at 100 deg.C for 10h, calcining in muffle furnace at 550 deg.C for 3h to obtain Co and Mo loaded CoMo/MgO-Al2O3A catalyst.
Taking the prepared CoMo/MgO-Al2O34g, 10mL of 0.5mol/L (N)H4)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 common tubular furnace to be activated in a hydrogen atmosphere at the activation temperature of 300 ℃, the heating rate of 1 ℃/s and the activation time of 60min to obtain the catalyst CoMoS/MgO-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 for 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), thus obtaining the proportion of a reactant and a product, and performing experiments for 2-8 hours respectively according to the method, thus obtaining 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 by 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 a comparison of the activity and selectivity of the catalysts prepared in different embodiments and comparative examples in catalyzing the hydrogenation reaction of toluene, and it can be found that the activity and selectivity of the catalysts in the hydrogenation reaction can be improved to different degrees by forming a composite carrier, presulfiding, and performing activation reduction using a rotary tube furnace.
TABLE 1
Figure BDA0002962416420000111

Claims (10)

1. A composite carrier monatomic catalyst for hydrogenation of organic hydrogen storage media is characterized in that: the catalyst comprises a composite carrier and an active component, wherein the active component comprises three components of Co, Mo and S, and the composite carrier is Al2O3And ZrO2、MgO、TiO2One or two of the components are compounded; active groupIs dispersed on the composite carrier in a single atom form.
2. The composite supported monatomic catalyst for hydrogenation of organic hydrogen storage media of claim 1, wherein: the loading amount of the active component on the composite carrier is 1-5 wt% calculated by the mass ratio of the active component to the composite carrier.
3. The preparation method of the composite carrier monatomic catalyst for hydrogenation of organic hydrogen storage media according to claim 1 or 2, characterized by comprising the steps of:
(1) sequentially dissolving aluminum and one or two metal salts of magnesium, zirconium and titanium in deionized water to obtain a solution I, adding polyethylene glycol 400 serving as a dispersing agent into the solution I, and stirring to obtain a mixed solution; dropwise adding ammonia water into the mixed solution, adjusting the pH value to 8-10, and continuously stirring for reaction; after the reaction is finished, filtering out a solid under reduced pressure, washing with deionized water, then placing into a constant-temperature water bath for crystallization, performing suction filtration after the crystallization is finished, then washing with absolute ethyl alcohol, and placing into an oven for drying to obtain a catalyst carrier precursor;
grinding the catalyst carrier precursor, and roasting in a muffle furnace to obtain a composite carrier;
(2) mixing Co (NO)3)2·6H2O and (NH)4)2MoO4Preparing a first impregnation liquid, adding the composite carrier obtained in the step (1) into the first impregnation liquid, standing, drying the composite carrier, and roasting in a muffle furnace to obtain a catalyst loaded with Co and Mo;
(3) will be (NH)4)2S2O3Dissolving the catalyst into deionized water to prepare a second impregnation solution, adding the Co and Mo loaded catalyst prepared in the step (2) into the second impregnation solution, standing, and drying the catalyst to obtain a pre-vulcanized catalyst;
then using a rotary tube furnace to activate the presulfurized catalyst at the temperature of 300-350 ℃ and H2And (3) activating for 50-80 min under the condition of 0.25-0.4Mpa of atmosphere to obtain the composite carrier monatomic catalyst for hydrogenation of the organic hydrogen storage medium.
4. The method for preparing the composite carrier monatomic catalyst for hydrogenation of organic hydrogen storage media according to claim 3, wherein in the step (1): one or two of magnesium, zirconium and titanium are called as other metal ions, wherein the molar concentration ratio of aluminum to the other metal ions is (1-5) to 1.
5. The method for preparing the composite carrier monatomic catalyst for hydrogenation of organic hydrogen storage media according to claim 3, wherein in the step (1): the volume ratio of the addition amount of the polyethylene glycol 400 to the solution I is 4 mL/L; the mass fraction of the ammonia water is 3-6 wt%; controlling the stirring time before ammonia water is dripped to be 10-15 min, and controlling the stirring time after ammonia water is dripped to be 40-50 min; the washing times of the deionized water and the absolute ethyl alcohol are respectively 3-5 times.
6. The method for preparing the composite carrier monatomic catalyst for hydrogenation of organic hydrogen storage media according to claim 3, wherein in the step (1): the temperature of the constant-temperature water bath during crystallization is 85-100 ℃, and the crystallization time is 3-5 h; the temperature of the oven is 90-120 ℃, and the drying time is 10 hours; the roasting temperature is 550 ℃ and the roasting time is 6 hours.
7. The method for preparing the composite carrier monatomic catalyst for hydrogenation of organic hydrogen storage media according to claim 3, wherein in the step (2): the mass percentage concentration of the first impregnation liquid is 1-6 wt%; loading the composite carrier by using an isometric impregnation method, wherein the volume ratio of the first impregnation liquid to the composite carrier 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 the composite carrier monatomic catalyst for hydrogenation of organic hydrogen storage media according to claim 3, wherein in the step (2): standing for 12-20 h; the drying temperature is 90-120 ℃, and the drying time is 8-15 h; the roasting temperature is 500-570 ℃, and the roasting time is 3-6 h.
9. The method for preparing the composite carrier monatomic catalyst for hydrogenation of organic hydrogen storage media according to claim 3, 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: and taking the second impregnation liquid according to the proportion of 1-3 mL of the second impregnation liquid per g of the catalyst loaded with Co and Mo.
10. The method for preparing the composite carrier monatomic catalyst for hydrogenation of organic hydrogen storage media according to claim 3, wherein in the step (3): standing for 4-5 h; the drying temperature is 80-90 ℃, and the drying time is 5-6 h.
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