CN113070077B - 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 PDFInfo
- Publication number
- CN113070077B CN113070077B CN202110241597.9A CN202110241597A CN113070077B CN 113070077 B CN113070077 B CN 113070077B CN 202110241597 A CN202110241597 A CN 202110241597A CN 113070077 B CN113070077 B CN 113070077B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrogen storage
- stirring
- temperature
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a composite carrier monatomic catalyst for hydrogenation of an organic hydrogen storage medium and a preparation method thereof 2 O 3 And ZrO 2 、MgO、TiO 2 One or two of the components are compounded; the active component is dispersed on the composite carrier in a single atom form. The loading capacity 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 furnace to realize the monatomic dispersion of the active component 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
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 based on noble metal catalysts, and although noble metals have better catalytic activity, the problem of higher cost is caused by the use of a large amount of noble metals, which causes certain difficulties for the large-scale popularization of the liquid organic hydrogen storage technology. The use of non-noble metal doping in the chinese patent application No. CN202010406445.5 discloses that the cost of the catalyst is reduced to a certain extent, but 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 single-atom 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 Al 2 O 3 And ZrO 2 、MgO、TiO 2 One 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 preferably 1 to 5wt% calculated by the mass ratio of the active component to the composite carrier.
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 the solid by using deionized water, then placing the solid into a constant-temperature water bath for crystallization, performing suction filtration after the crystallization is finished, then washing the solid by using absolute ethyl alcohol, and placing the washed solid into a drying 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 ·6H 2 O and (NH) 4 ) 2 MoO 4 Preparing 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 ) 2 S 2 O 3 Dissolving 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 a rotary tube furnace is used for activating the presulfurized catalyst at the temperature of 300-350 ℃ and H 2 Activating for 50-80 min under the condition of 0.25-0.4Mpa pressure to obtain the composite carrier monatomic catalyst for hydrogenation of the organic hydrogen storage medium.
Preferably, in step (1): one or two of the three types of magnesium, zirconium and titanium are called 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 4mL/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 10h; 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 liquid 3 ) 2 ·6H 2 O and (NH) 4 ) 2 MoO 4 The mass ratio of the components 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: taking the second impregnation liquid according to the proportion of 1-3 mL of the second impregnation liquid per gram 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 30r/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 the hydrogenation of the organic hydrogen storage medium as an example, specifically, 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, then nitrogen is continuously introduced to replace the air existing in the dynamic reaction kettle, after 5min, hydrogen is introduced to replace the nitrogen in the dynamic reaction kettle, the replacement is carried out for 10min, the gas outlet is closed, the hydrogen pressure is adjusted to 8-12MPa, then the temperature is increased to 160-220 ℃, and the reaction is carried out 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 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 supported 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 toluene of the catalyst can reach 90 percent, and the selectivity of 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 Al 2 O 3 And ZrO 2 、MgO、TiO 2 One 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 out 3 ) 3 ·9H 2 O and 3.46g of MgSO 4 ·H 2 Dissolving 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 5wt% 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 adopting vacuum filtration, washing the obtained precipitate with deionized water for 3 times, then putting the precipitate into a water bath with the constant temperature of 90 ℃ for crystallization for 4 hours, washing the precipitate with absolute ethyl alcohol for 3 times after the crystallization is finished, and then putting the precipitate into an oven with the temperature of 100 ℃ for drying 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-Al 2 O 3 。
0.218g Co (NO) was weighed out 3 ) 2 ·6H 2 O and 0.343g (NH) 4 ) 2 MoO 4 Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared composite carrier MgO-Al into the immersion liquid 2 O 3 Standing at room temperatureOver night, drying at 100 ℃ for 10h, placing in a muffle furnace to roast at 550 ℃ for 3h to obtain Co and Mo loaded CoMo/MgO-Al 2 O 3 A catalyst.
Taking the prepared CoMo/MgO-Al 2 O 3 10mL of (NH) 0.5mol/L catalyst (4 g) was added 4 ) 2 S 2 O 3 Standing the impregnation solution 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 medium 2 O 3 。
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 after the reaction is carried out for 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, carrying out qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry) to obtain the proportion of a reactant and a product, and carrying out experiments for 2-8 hours respectively according to the method to obtain the effect of catalyzing the hydrogenation reaction of the organic hydrogen storage medium by using the catalyst.
Example 2
18.75g of Al (NO) are weighed out 3 ) 3 ·9H 2 O and 8.19g of Zr (CH) 3 COO) 4 Dissolving 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 5wt% 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 ZrO 2 -Al 2 O 3 。
0.218g Co (NO) was weighed out 3 ) 2 ·6H 2 O and 0.343g (NH) 4 ) 2 MoO 4 Adding into 10mL of water to prepare an impregnation solution, and adding 5g of the prepared composite carrier ZrO into the impregnation solution 2 -Al 2 O 3 Standing at room temperature overnight, drying at 100 deg.C for 10h, and calcining in muffle furnace at 550 deg.C for 3h to obtain Co and Mo loaded CoMo/ZrO 2 -Al 2 O 3 A catalyst.
Taking the prepared CoMo/ZrO 2 -Al 2 O 3 10mL of (NH) 0.5mol/L catalyst (4 g) was added 4 ) 2 S 2 O 3 Standing the impregnation solution 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 medium 2 -Al 2 O 3 。
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 out 3 ) 3 ·9H 2 O and 6g of TiSO 4 Dissolving 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 5wt% 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 crystallizing in water bath at constant temperature of 90 deg.CDissolving for 4h, washing for 3 times by using absolute ethyl alcohol again after crystallization is finished, and then drying 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 550 ℃ to obtain the composite carrier TiO 2 -Al 2 O 3 。
Weigh 0.218g Co (NO) 3 ) 2 ·6H 2 O and 0.343g (NH) 4 ) 2 MoO 4 Adding into 10mL water to prepare a maceration extract, and adding 6g of the prepared composite carrier TiO 2 ·Al 2 O 3 Standing at room temperature overnight, drying at 100 deg.C for 10h, and calcining in muffle furnace at 550 deg.C for 3h to obtain Co and Mo loaded CoMo/TiO 2 -Al 2 O 3 A catalyst.
Taking the prepared CoMo/TiO 2 -Al 2 O 3 10mL of (NH) 0.5mol/L catalyst (4 g) was added 4 ) 2 S 2 O 3 Standing the impregnation solution 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 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 medium 2 -Al 2 O 3 。
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 after the reaction is carried out for 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, carrying out qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry) to obtain the proportion of a reactant and a product, and carrying out experiments for 2-8 hours respectively according to the method to obtain the effect of catalyzing the hydrogenation reaction of the organic hydrogen storage medium by using the catalyst.
Example 4
18.75g of Al (NO) are weighed out 3 ) 3 ·9H 2 O and 4.1g of Zr (CH 3 COO) 4 And 1.73g of MgSO 4 ·H 2 Dissolving O in 500mL deionized water, stirring at 300r/min at normal temperature for 10min, and adding 2mL polymerAnd using ethylene glycol 400 as a dispersing agent, and continuously stirring for 15min to obtain a mixed solution. Dropwise adding ammonia water with the mass fraction of 5wt% 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 ZrO 2 -MgO-Al 2 O 3 。
Weigh 0.218g Co (NO) 3 ) 2 6H2O and 0.343g (NH) 4 ) 2 MoO 4 Adding into 10mL of water to prepare an impregnation solution, and adding 5g of the prepared composite carrier ZrO into the impregnation solution 2 -MgO-Al 2 O 3 Standing 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/ZrO 2 -MgO-Al 2 O 3 A catalyst.
Taking the prepared CoMo/ZrO 2 -MgO-Al 2 O 3 4g, 10mL of (NH) 0.5mol/L 4 ) 2 S 2 O 3 Standing the impregnation solution at room temperature for 4h, and drying at 90 ℃ for 4h to obtain the pre-vulcanized catalyst. The catalyst is put into a rotary tube furnace to be activated in hydrogen atmosphere at the activation temperature of 300 ℃, the rotation speed of 30r/min and the activation time of 60min, and the catalyst CoMoS/ZrO for hydrogenation of the organic hydrogen storage medium is obtained 2 -MgO-Al 2 O 3 。
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 out 3 ) 3 ·9H 2 O and 4.1g of Zr (CH 3 COO) 4 And 3g of TiSO 4 Dissolving 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 5wt% 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 ZrO 2 -TiO 2 -Al 2 O 3 。
Weigh 0.218g Co (NO) 3 ) 2 ·6H 2 O and 0.343g (NH) 4 ) 2 MoO 4 Adding into 10mL of water to prepare an impregnation solution, and adding 5g of the prepared composite carrier ZrO into the impregnation solution 2 -TiO 2 -Al 2 O 3 Standing 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/ZrO 2 -TiO 2 -Al 2 O 3 A catalyst.
Taking the prepared CoMo/ZrO 2 -TiO 2 -Al 2 O 3 4g, 10mL of (NH) 0.5mol/L 4 ) 2 S 2 O 3 Standing the impregnation solution 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 medium 2 -TiO 2 -Al 2 O 3 。
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 after the reaction is carried out for 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, carrying out qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry) to obtain the proportion of a reactant and a product, and carrying out experiments for 2-8 hours respectively according to the method to obtain the effect of catalyzing the hydrogenation reaction of the organic hydrogen storage medium by using the catalyst.
Example 6
18.75g of Al (NO) are weighed out 3 ) 3 ·9H 2 O and 1.73g MgSO 4 ·H 2 O and 3g of TiSO 4 Dissolving in 500mL of deionized water, stirring at the normal temperature 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 5wt% 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-TiO 2 -Al 2 O 3 。
Weigh 0.655g Co (NO) 3 ) 2 ·6H 2 O and 0.343g (NH) 4 ) 2 MoO 4 Adding into 10mL water to obtain a soaking solution, and adding 5g of the prepared MgO-TiO 2 -Al 2 O 3 Standing 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-TiO 2 -Al 2 O 3 A catalyst.
Taking the prepared CoMo/MgO-TiO 2 -Al 2 O 3 4g, 10mL of 0.5mol/L (NH) was added 4 ) 2 S 2 O 3 Standing the impregnation solution at room temperature for 4h, and drying at 90 ℃ for 4h to obtain the pre-vulcanized catalyst. Putting it into rotary tube furnace to activate in hydrogen atmosphereActivating at 300 deg.C, heating rate of 1 deg.C/s, rotation speed of 30r/min, activation pressure of 0.25-0.4Mpa, and activation time of 60min to obtain catalyst CoMoS/MgO-TiO for hydrogenation of organic hydrogen storage medium 2 -Al 2 O 3 。
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 out 3 ) 3 ·9H 2 O and 3.46g of MgSO 4 ·H 2 Dissolving 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 5wt% 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 adopting vacuum filtration, washing the obtained precipitate with deionized water for 3 times, then putting the precipitate into a water bath with the constant temperature of 90 ℃ for crystallization for 4 hours, washing the precipitate with absolute ethyl alcohol for 3 times after the crystallization is finished, and then putting the precipitate into an oven with the temperature of 100 ℃ for drying 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-Al 2 O 3 。
0.109g of Co (NO) was weighed out 3 ) 2 ·6H 2 O and 0.343g (NH) 4 ) 2 MoO 4 Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared composite carrier MgO-Al into the immersion liquid 2 O 3 Standing 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-Al 2 O 3 A catalyst.
Taking the obtainedCoMo/MgO-Al 2 O 3 10mL of (NH) 0.5mol/L catalyst (4 g) was added 4 ) 2 S 2 O 3 Standing the impregnation solution 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 medium 2 O 3 。
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 out 3 ) 3 ·9H 2 O and 3.46g of MgSO 4 ·H 2 Dissolving 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 5wt% 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-Al 2 O 3 。
Weigh 0.436g Co (NO) 3 ) 2 ·6H 2 O and 0.343g (NH) 4 ) 2 MoO 4 Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared composite carrier MgO-Al into the immersion liquid 2 O 3 Standing 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-Al 2 O 3 A catalyst.
Taking the prepared CoMo/MgO-Al 2 O 3 4g, 10mL of (NH) 0.5mol/L 4 ) 2 S 2 O 3 Standing the impregnation solution 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 CoMoS/MgO-Al catalyst for hydrogenation of organic hydrogen storage medium 2 O 3 。
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 the metal species can all achieve 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 out 3 ) 3 ·9H 2 Dissolving 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 5wt% 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 Al 2 O 3 And (3) a carrier.
Weigh 0.218g Co (NO) 3 ) 2 ·6H 2 O and 0.343g (NH) 4 ) 2 MoO 4 Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared Al into the immersion liquid 2 O 3 And (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/Al 2 O 3 4g, 10mL of (NH) 0.5mol/L 4 ) 2 S 2 O 3 Standing the impregnation solution 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 medium 2 O 3 。
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 out 3 ) 3 ·9H 2 O and 3.46g of MgSO 4 ·H 2 Dissolving O in 500mL of deionized water, stirring at the normal temperature 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 5wt% 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-Al 2 O 3 。
Weigh 0.218g Co (NO) 3 ) 2 ·6H 2 O and 0.343g (NH) 4 ) 2 MoO 4 Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared composite carrier MgO-Al into the immersion liquid 2 O 3 Standing 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-Al 2 O 3 A catalyst.
4g of CoMo/MgO-Al was taken 2 O 3 The 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/MgO-Al which is not vulcanized and is used for hydrogenating the organic hydrogen storage medium is obtained 2 O 3 。
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 after the reaction is carried out for 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, carrying out qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry) to obtain the proportion of a reactant and a product, and carrying out experiments for 2-8 hours respectively according to the method to obtain the effect of catalyzing the hydrogenation reaction of the organic hydrogen storage medium by using the catalyst.
Comparative example 3
18.75g of Al (NO) are weighed out 3 ) 3 ·9H 2 O and 3.46g of MgSO 4 ·H 2 Dissolving 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 5wt% 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-Al 2 O 3 。
Weigh 0.218g Co (NO) 3 ) 2 ·6H 2 O and 0.343g (NH) 4 ) 2 MoO 4 Adding into 10mL water to obtain an immersion liquid, and adding 5g of the prepared composite carrier MgO-Al into the immersion liquid 2 O 3 Standing 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-Al 2 O 3 A catalyst.
Taking the prepared CoMo/MgO-Al 2 O 3 4g, 10mL of 0.5mol/L (NH) was added 4 ) 2 S 2 O 3 Standing the impregnation solution 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 medium 2 O 3 。
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 after the reaction is carried out for 1h, cooling the high-pressure reaction kettle to room temperature, taking out a liquid-phase product of the reaction, carrying out qualitative and quantitative analysis by using GC-MS (gas chromatography-mass spectrometry) to obtain the proportion of a reactant and a product, and carrying out experiments for 2-8 hours respectively according to the method to obtain the effect of catalyzing the hydrogenation reaction of the organic hydrogen storage medium by using the catalyst.
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
Claims (1)
1. A preparation method of a catalyst for hydrogenation of an organic hydrogen storage medium is characterized by comprising the following steps:
18.75g of Al (NO) are weighed out 3 ) 3 ·9H 2 O and 4.1g of Zr (CH 3 COO) 4 And 3g of TiSO 4 Dissolving in 500mL of deionized water, stirring at the speed of 300r/min at normal temperature 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 5wt% into the mixed solution under the stirring state, adjusting the pH to 9.0, keeping stirring for reacting for 40min, and then closing stirring; separating out precipitate by vacuum filtration, washing the obtained precipitate with deionized water for 3 times, crystallizing in a constant-temperature 90 ℃ water bath for 4 hours, washing with absolute ethyl alcohol for 3 times after crystallization is finished, and drying in a 100 ℃ oven for 10 hours to obtain a catalyst carrier precursor; grinding the precursor of the catalyst carrier into powder and placingRoasting the mixture for 6 hours at 550 ℃ in a muffle furnace to obtain the composite carrier ZrO 2 -TiO 2 -Al 2 O 3 ；
Weigh 0.218g Co (NO) 3 ) 2 ·6H 2 O and 0.343g (NH) 4 ) 2 MoO 4 Adding into 10mL of water to prepare an impregnation solution, and adding 5g of the prepared composite carrier ZrO into the impregnation solution 2 -TiO 2 -Al 2 O 3 Standing 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/ZrO 2 -TiO 2 -Al 2 O 3 A catalyst;
taking the prepared CoMo/ZrO 2 -TiO 2 -Al 2 O 3 4g, 10mL of 0.5mol/L (NH) was added 4 ) 2 S 2 O 3 Standing the impregnation liquid for 4h at room temperature, and drying for 4h at 90 ℃ to obtain a 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 medium 2 -TiO 2 -Al 2 O 3 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110241597.9A CN113070077B (en) | 2021-03-04 | 2021-03-04 | Composite carrier single-atom catalyst for hydrogenation of organic hydrogen storage medium and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110241597.9A CN113070077B (en) | 2021-03-04 | 2021-03-04 | Composite carrier single-atom catalyst for hydrogenation of organic hydrogen storage medium and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113070077A CN113070077A (en) | 2021-07-06 |
| CN113070077B true CN113070077B (en) | 2023-02-28 |
Family
ID=76609899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110241597.9A Active CN113070077B (en) | 2021-03-04 | 2021-03-04 | Composite carrier single-atom catalyst for hydrogenation of organic hydrogen storage medium and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113070077B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2758957A (en) * | 1955-02-25 | 1956-08-14 | Shell Dev | Hydrogenation of aromatics and sulfurbearing hydrocarbon oils and catalysts therefor |
| CN110841630A (en) * | 2019-11-29 | 2020-02-28 | 中国科学院上海高等研究院 | Organic hydrogen storage material hydrogenation and dehydrogenation catalyst and preparation method thereof |
| CN110935470A (en) * | 2019-11-25 | 2020-03-31 | 北京化工大学 | Preparation method of exhaust gas purification catalyst |
-
2021
- 2021-03-04 CN CN202110241597.9A patent/CN113070077B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2758957A (en) * | 1955-02-25 | 1956-08-14 | Shell Dev | Hydrogenation of aromatics and sulfurbearing hydrocarbon oils and catalysts therefor |
| CN110935470A (en) * | 2019-11-25 | 2020-03-31 | 北京化工大学 | Preparation method of exhaust gas purification catalyst |
| CN110841630A (en) * | 2019-11-29 | 2020-02-28 | 中国科学院上海高等研究院 | Organic hydrogen storage material hydrogenation and dehydrogenation catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| "A rational interpretation of improved catalytic performances of additive-impregnated dried CoMo hydrotreating catalysts: a combined theoretical and experimental study";V. Costa等;《Catal. Sci. Technol》;20121011;第3卷(第140期);140-151 * |
| "硫代硫酸铵对CoMo和NiMoP催化剂的预硫化";葛晖等;《催化学报》;20100131;第31卷(第1期);18-20 * |
| "钼基催化材料的改性及其催化4,6-二甲基二苯并噻吩加氢脱硫反应性能的研究";许愿;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》;20200615(第06期);B017-97 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113070077A (en) | 2021-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101502802B (en) | Preparation method of catalyst for continuous production of succinic anhydride from hydrogenation of maleic anhydride | |
| CN113070061B (en) | Rare earth element doped monatomic catalyst for organic hydrogen storage medium dehydrogenation and preparation method thereof | |
| CN109692713A (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and the preparation method and application thereof | |
| CN114797912B (en) | Dehydrogenation catalyst and preparation method thereof | |
| CN109529821B (en) | Palladium-based catalyst for thermal catalysis of formaldehyde degradation | |
| CN109420517B (en) | Method for preparing higher hydrocarbon by methane low-temperature conversion | |
| CN104437467A (en) | Hydrogenation catalyst, application of hydrogenation catalyst, dehydrogenation catalyst and application of dehydrogenation catalyst | |
| CN113070078B (en) | Rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst and preparation method thereof | |
| CN108816221A (en) | A kind of aluminium oxide is the preparation method of the ruthenium-based ammonia synthetic catalyst of carrier | |
| CN113398926A (en) | For CO2Pt/In for preparing methanol by catalytic hydrogenation2O3Catalyst and preparation method thereof | |
| CN114768859B (en) | Nickel-silicon catalyst suitable for methane dry reforming and preparation method thereof | |
| CN109806874A (en) | A kind of preparation method and application of carbon dioxide methanation nickel-based multimetallic catalyst | |
| CN113477252A (en) | Preparation method and application of composite porous catalyst simultaneously containing titanium and other transition metals | |
| CN113058613B (en) | Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof | |
| CN110339857A (en) | A kind of nickel-base catalyst and its preparation method and application that thermal stability is high | |
| CN113070077B (en) | Composite carrier single-atom catalyst for hydrogenation of organic hydrogen storage medium and preparation method thereof | |
| KR20230024393A (en) | Manufacturing method of copper-based hydrogenation catalyst, catalyst produced thereby and applications | |
| CN113070058B (en) | Composite carrier single-atom catalyst for organic hydrogen storage medium dehydrogenation and preparation method thereof | |
| CN110732327A (en) | carbon material-coated nickel catalyst and method for preparing primary amine compound by using same | |
| CN102441388B (en) | Preparation method for cobalt-base Fischer Tropsch synthetic catalyst with high stability | |
| CN114054023B (en) | Preparation method and application of alloy monoatomic catalyst | |
| CN109718843A (en) | A kind of preparation and application of novel carbon dioxide methanation catalyst | |
| CN102389832B (en) | Catalyst for preparing C5 and C6 alkanes by hydrogenating high-activity sorbierite water phase, and preparation method of catalyst | |
| CN109796305B (en) | Method for preparing cyclohexanol by adopting composite catalyst | |
| CN114870853A (en) | Core-shell catalyst for preparing cyclohexanol by catalyzing selective hydrogenation and deoxidation of guaiacol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhao Hong Inventor before: Zhang Jie Inventor before: Zhao Hong |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |