CN113926462A - Hydrogenation catalytic material, preparation method and application - Google Patents
Hydrogenation catalytic material, preparation method and application Download PDFInfo
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- CN113926462A CN113926462A CN202111391419.0A CN202111391419A CN113926462A CN 113926462 A CN113926462 A CN 113926462A CN 202111391419 A CN202111391419 A CN 202111391419A CN 113926462 A CN113926462 A CN 113926462A
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 54
- 239000001257 hydrogen Substances 0.000 claims description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 40
- 238000001354 calcination Methods 0.000 claims description 20
- 238000003860 storage Methods 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000011265 semifinished product Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 8
- 239000007769 metal material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 41
- 239000000047 product Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 13
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 12
- 229910003296 Ni-Mo Inorganic materials 0.000 description 12
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000010926 purge Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a hydrogenation catalytic material, a preparation method and application thereof, wherein the catalyst comprises a carrier and a catalyst, the load of the catalyst on the carrier is 5-12.5 wt.%, the catalyst comprises a nickel element and a molybdenum element, and the mass ratio of the nickel element to the molybdenum element is (1-4): 1. the catalyst provided by the invention adopts non-noble metal materials, so that the cost of the product is effectively reduced while better catalytic performance is obtained.
Description
Technical Field
The invention relates to a liquid hydrogen storage catalysis technology, in particular to a hydrogenation catalysis material, a preparation method and application.
Background
The hydrogen energy is a clean and efficient energy carrier with rich resources and high energy density, and the large-scale application of the hydrogen energy can relieve the problems of shortage of traditional fossil energy, environmental pollution, greenhouse effect and the like, and is vital to the sustainable development of the human society.
At present, the commonly used hydrogen energy storage modes comprise three modes of liquid hydrogen storage, high-pressure gaseous hydrogen storage and solid hydrogen storage. Pressurized hydrogen storage is the earliest research and application, but the hydrogen storage technology has low hydrogen storage mass density, is easy to generate hydrogen embrittlement phenomenon and has potential danger; low-temperature liquid hydrogen storage requires a liquefaction storage tank with excellent heat insulation performance and has strict requirements on materials; although solid hydrogen storage has a large volume storage capacity, the hydrogen storage material can be deteriorated, hydrogen damage, hydrogen corrosion and the like are generated, and the recycling of the hydrogen carrier is influenced. The research of liquid phase organic hydrogen storage technology in the 80 s of the 20 th century utilizes unsaturated bonds in organic matters to realize the storage and release of hydrogen. Compared with the hydrogen storage modes, the hydrogen carrier used for liquid phase organic hydrogen storage is similar to gasoline in property, the existing oil transportation equipment can be utilized, the mass hydrogen storage density is high (7.19% of benzene and 6.18% of toluene), and the hydrogen storage reaction is highly reversible. In addition, the hydrogen carrier (such as benzyl toluene, dibenzyl toluene, N-ethyl carbazole and the like) has stable physicochemical properties, can be recycled and has the service life of about 20 years.
The addition and dehydrogenation catalyst used in liquid phase organic hydrogen storage technology is Ru/Pt supported on Al2O3、TiO2、SiO2Molecular sieves, activated carbon and the like, but the noble metal catalyst is expensive, so that the industrial production application of the noble metal catalyst is limited to a great extent.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a hydrogenation catalytic material, a preparation method and application thereof.
In order to achieve the above object, an embodiment of the present invention provides a hydrocatalytic material comprising a carrier and a catalyst, wherein the loading of the catalyst on the carrier is 5 to 12.5 wt.%, wherein the catalyst comprises a nickel element and a molybdenum element, and the mass ratio of the nickel element to the molybdenum element is (1 to 4): 1.
in one or more embodiments of the invention, the support is Al2O3Supports or zirconia supports or zeolite supportsAnd (3) a body.
In one or more embodiments of the present invention, a method for preparing a hydrocatalytic material comprises the steps of: A. preparing a proper amount of molybdenum source solution, soaking the carrier with the molybdenum source solution, drying, and calcining in the air atmosphere to obtain a catalyst precursor I; B. preparing a proper amount of nickel source solution, soaking the catalyst semi-finished product with the nickel source solution, drying, and calcining in an air atmosphere to obtain a catalyst precursor II; C. and calcining the catalyst precursor II in a hydrogen atmosphere to obtain the catalyst.
In one or more embodiments of the present invention, the molybdenum source solution in step a is a molybdate solution, and the solvent of the solution is ultrapure water or absolute ethyl alcohol.
In one or more embodiments of the present invention, the nickel solution in step B is an aqueous solution of nickel nitrate or an ethanol solution, and the solvent of the solution is ultrapure water or absolute ethanol.
In one or more embodiments of the present invention, the drying in step a or step B is: drying at 80-120 deg.C for 18-36 h.
In one or more embodiments of the invention, the calcination in step a or step B is both: calcining at the temperature of 400 ℃ for 4-6h under the air atmosphere.
In one or more embodiments of the invention, the hydrogen atmosphere in step C is 40-60mL/min in a tube furnace.
In one or more embodiments of the present invention, the calcination in step C is 500-550 ℃ for 4-6 h.
In one or more embodiments of the invention, the hydrogenation catalytic material as described above is used for hydrogenation in liquid hydrogen storage.
In one or more embodiments of the present invention, the hydrogenation is specifically applied as follows: controlling the dosage of the catalyst to be 5-10% of the mass of the carrier; emptying the qualified reaction device (such as the reaction device passes pressure maintaining air tightness inspection in advance); and (3) carrying out reaction under the conditions of heating and stirring until the reaction is finished. Preferably, the reaction is terminated by monitoring the pressure drop across the reactor during the reaction, and the termination of the reaction is indicated by a steady (no further decrease) pressure. Preferably, the reaction temperature is 180-. Preferably, the stirring speed is 1300-.
Compared with the prior art, the hydrogenation catalytic material, the preparation method and the application have the following advantages:
the existing catalyst is mostly loaded by noble metals and is expensive, and the catalyst in the patent is loaded by alumina which is loaded by Ni and Mo non-noble metals, so that the economic cost is saved;
has the advantages that:
the preparation cost of the catalyst is reduced, the cost of the noble metal catalyst is high, Ni and Mo used in the experiment are non-noble metal catalysts, but the catalytic performance is better compared with the noble metal catalyst in the aspect of hydrogenation time;
the carrier alumina has better adaptability, alumina carriers with different pore sizes can be selected according to reaction requirements, the price is low, and the synthesis cost and the economic cost are saved;
the catalyst is a Ni and Mo bimetal, and plays a role in synergy, so that the hydrogenation efficiency is improved.
Drawings
FIG. 1 is a pressure-time curve for different ratios of catalyst according to one embodiment of the present invention;
FIG. 2 is an XRD pattern for catalysts of different proportions according to an embodiment of the present invention;
FIG. 3 is a graph of GC-MS of a hydrogen carrier after hydrogenation of benzyltoluene in accordance with one embodiment of the present invention.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Example 1
As shown in fig. 1 to 3, the hydrogenation catalytic material according to the preferred embodiment of the present invention:
the hydrogen carrier (liquid phase organic matter) is benzyl toluene, and the hydrogenation catalytic material is Ni-Mo/Al2O3。
Preparing a hydrogenation catalytic material:
1) preparing an ammonium molybdate solution with a certain concentration, wherein the solvent is ultrapure water to obtain a solution A;
2) soaking the solution A in Al by an isovolumetric soaking method2O3Obtaining a precursor B in the carrier;
3) placing the precursor B in an oven, and drying for 24 hours at 100 ℃ to obtain a dried product C;
4) calcining the product C in a muffle furnace in air atmosphere at 350 ℃ for 4h to obtain a product D;
5) preparing a nickel nitrate solution with a certain concentration, wherein the solvent is ultrapure water to obtain a solution E;
6) similarly, loading Ni on the product D by repeating the steps 2), 3) and 4) to obtain a product F;
7) calcining the product F in a tubular furnace at the temperature of 500 ℃ for 4 hours in the hydrogen atmosphere at the flow rate of 40-60mL/min to prepare the catalyst named as Ni-Mo/Al2O3。
Hydrogenation test conditions:
hydrogenation equipment: the high-temperature high-pressure reaction kettle comprises a mechanical stirring device, is provided with a parameter panel for temperature, pressure and reaction time, is connected with a computer through a data line and can record the numerical values of all parameters, and the frequency is 13 s/time. The reaction kettle comprises an air inlet and an air outlet, the ball valve controls the switch, the air inlet can be filled with nitrogen/hydrogen, and the air outlet is connected with an emptying pipeline.
Hydrogenation experiment steps:
feeding: the reactor was charged with 40g of benzyltoluene (abbreviated as MBT) and 5 wt.% -MBT (referring to catalyst at 5% of the mass of MBT) of Ni-Mo/Al2O3Catalyst, mass 2 g;
pressure maintaining: installing a reaction kettle and a pipeline, maintaining the pressure of nitrogen (about 2-3MPa) in the reaction kettle for 30min, and regarding the pressure as no air leakage when the pressure is almost kept unchanged;
and (3) replacement: in order to ensure that the air in the kettle is exhausted, firstly purging for 3 times by using nitrogen (about 1-2MPa), then purging for 3 times by using hydrogen (about 1-2MPa), wherein the gauge pressure is 0MPa after the air is exhausted, and closing an inlet valve and an outlet valve;
heating: setting the reaction temperature to be 200 ℃, the stirring speed to be 1500rpm, starting to increase the furnace temperature, and entering a heating state;
reaction: when the temperature is kept at about 200 ℃, hydrogen (7-8MPa) is introduced to start the hydrogenation reaction, and the computer records the pressure drop and the time change.
And (4) ending: and when the pressure to be measured does not change any more, closing the heating, stirring and inlet and outlet valves, and stopping the reaction.
1) The hydrogenation effect of the catalysts with different proportions is as follows:
2) 7.5% Ni-2.5% Mo/Al is used2O3After the catalyst is subjected to hydrogenation reaction, the GC-MS peak and the product ratio of the hydrogenated benzyltoluene on the hydrogen carrier are shown in fig. 3 (since all the catalysts in the above four proportions are completely hydrogenated, only one proportion is selected in this example), wherein benzylbenzene is a trace impurity contained in the raw benzyltoluene, and the hydrogenation is also completely performed.
Example 2
The hydrocatalytic material according to a preferred embodiment of the present invention:
the hydrogen carrier (liquid phase organic matter) is benzyl toluene, and the hydrogenation catalytic material is Ni-Mo/zirconia.
Preparing a hydrogenation catalytic material:
1) preparing a sodium molybdate solution with a certain concentration, wherein the solvent is ultrapure water to obtain a solution A;
2) soaking the solution A in a zirconium oxide carrier to obtain a precursor B;
3) placing the precursor B in an oven, and drying at 80 ℃ for 18h to obtain a dried product C;
4) calcining the product C in a muffle furnace in air atmosphere at 400 ℃ for 5 hours to obtain a product D;
5) preparing a nickel nitrate solution with a certain concentration, wherein the solvent is ultrapure water to obtain a solution E;
6) similarly, loading Ni on the product D by repeating the steps 2), 3) and 4) to obtain a product F;
7) and putting the product F into a tubular furnace, calcining for 4 hours at 500 ℃ in a hydrogen atmosphere at the flow rate of 40-60mL/min to prepare the catalyst named as Ni-Mo/zirconia.
Hydrogenation test conditions:
hydrogenation equipment: the high-temperature high-pressure reaction kettle comprises a mechanical stirring device, is provided with a parameter panel for temperature, pressure and reaction time, is connected with a computer through a data line and can record the numerical values of all parameters, and the frequency is 13 s/time. The reaction kettle comprises an air inlet and an air outlet, the ball valve controls the switch, the air inlet can be filled with nitrogen/hydrogen, and the air outlet is connected with an emptying pipeline.
Hydrogenation experiment steps:
feeding: the reaction kettle was charged with 40g of benzyltoluene (abbreviated as MBT) and 7.5wt. -MBT of Ni-Mo/zirconia catalyst with a mass of 3 g;
pressure maintaining: installing a reaction kettle and a pipeline, maintaining the pressure of nitrogen (about 2-3MPa) in the reaction kettle for 30min, and regarding the pressure as no air leakage when the pressure is almost kept unchanged;
and (3) replacement: in order to ensure that the air in the kettle is exhausted, firstly purging for 3 times by using nitrogen (about 1-2MPa), then purging for 3 times by using hydrogen (about 1-2MPa), wherein the gauge pressure is 0MPa after the air is exhausted, and closing an inlet valve and an outlet valve;
heating: setting the reaction temperature to be 180 ℃, the stirring speed to be 1400rpm, starting to increase the furnace temperature, and entering a heating state;
reaction: when the temperature is kept at about 180 ℃, hydrogen (7-8MPa) is introduced to start the hydrogenation reaction, and the computer records the pressure drop and the time change.
And (4) ending: and when the pressure to be measured does not change any more, closing the heating, stirring and inlet and outlet valves, and stopping the reaction.
1) The hydrogenation effect of the catalysts with different proportions is as follows:
example 3
Hydrocatalytic material according to a preferred embodiment of the present invention
The hydrogen carrier (liquid phase organic matter) is benzyl toluene, and the hydrogenation catalytic material is Ni-Mo/Al2O3。
Preparing a hydrogenation catalytic material:
1) preparing a potassium molybdate solution with a certain concentration, wherein the solvent is absolute ethyl alcohol to obtain a solution A;
2) soaking the solution A in a zeolite carrier to obtain a precursor B;
3) placing the precursor B in an oven, and drying at 120 ℃ for 36h to obtain a dried product C;
4) calcining the product C in a muffle furnace in air atmosphere at 300 ℃ for 6 hours to obtain a product D;
5) preparing a nickel nitrate solution with a certain concentration, wherein the solvent is absolute ethyl alcohol to obtain a solution E;
6) similarly, loading Ni on the product D by repeating the steps 2), 3) and 4) to obtain a product F;
7) calcining the product F in a tubular furnace at the temperature of 500 ℃ for 4 hours in the hydrogen atmosphere at the flow rate of 40-60mL/min to prepare the catalyst named as Ni-Mo/Al2O3。
Hydrogenation test conditions:
hydrogenation equipment: the high-temperature high-pressure reaction kettle comprises a mechanical stirring device, is provided with a parameter panel for temperature, pressure and reaction time, is connected with a computer through a data line and can record the numerical values of all parameters, and the frequency is 13 s/time. The reaction kettle comprises an air inlet and an air outlet, the ball valve controls the switch, the air inlet can be filled with nitrogen/hydrogen, and the air outlet is connected with an emptying pipeline.
Hydrogenation experiment steps:
feeding: the reaction kettle was charged with 40g of benzyltoluene (abbreviated as MBT) and 10 wt.% -MBT of Ni-Mo/zeolite catalyst with a mass of 4 g;
pressure maintaining: installing a reaction kettle and a pipeline, maintaining the pressure of nitrogen (about 2-3MPa) in the reaction kettle for 30min, and regarding the pressure as no air leakage when the pressure is almost kept unchanged;
and (3) replacement: in order to ensure that the air in the kettle is exhausted, firstly purging for 3 times by using nitrogen (about 1-2MPa), then purging for 3 times by using hydrogen (about 1-2MPa), wherein the gauge pressure is 0MPa after the air is exhausted, and closing an inlet valve and an outlet valve;
heating: setting the reaction temperature to 190 ℃, the stirring speed to 1300rpm, starting to increase the furnace temperature, and entering a heating state;
reaction: when the temperature is kept at about 190 ℃, hydrogen (7-8MPa) is introduced to start the hydrogenation reaction, and the computer records the pressure drop and the time change.
And (4) ending: and when the pressure to be measured does not change any more, closing the heating, stirring and inlet and outlet valves, and stopping the reaction.
1) The hydrogenation effect of the catalysts with different proportions is as follows:
| serial number | Catalyst and process for preparing same | Hydrogenation time/ |
| Sample | ||
| 1 | 2.5% Ni-2.5% Mo/Zeolite | 39.0 |
| |
5.0% Ni-2.5% Mo/Zeolite | 35.5 |
| |
7.5% Ni-2.5% Mo/Zeolite | 29.0 |
| Sample No. 4 | 10.0% Ni-2.5% Mo/zeolite | 32.0 |
| Sample No. 5 | 7.5% Ni/Zeolite | 50.0 |
| Sample No. 6 | 2.5% Mo/Zeolite | Infinity(s) |
Example 4
The hydrocatalytic material according to a preferred embodiment of the present invention:
the hydrogen carrier (liquid phase organic matter) is benzyl toluene, and the hydrogenation catalytic material is Ni-Mo/Al2O3。
Preparing a hydrogenation catalytic material:
1) preparing an ammonium molybdate solution with a certain concentration, wherein the solvent is ultrapure water or absolute ethyl alcohol to obtain a solution A;
2) soaking the solution A in Al by an isovolumetric soaking method2O3Support (different gauges of Al for different samples according to the following Table)2O3Carrier) to obtain a precursor B;
3) placing the precursor B in an oven, and drying for 24 hours at 100 ℃ to obtain a dried product C;
4) calcining the product C in a muffle furnace in air atmosphere at 350 ℃ for 4h to obtain a product D;
5) preparing a nickel nitrate solution with a certain concentration, wherein the solvent is ultrapure water or absolute ethyl alcohol to obtain a solution E;
6) similarly, loading Ni on the product D by repeating the steps 2), 3) and 4) to obtain a product F;
7) calcining the product F in a tubular furnace at the temperature of 500 ℃ for 4 hours in the hydrogen atmosphere at the flow rate of 40-60mL/min to prepare the catalyst named as Ni-Mo/Al2O3。
Hydrogenation test conditions:
hydrogenation equipment: the high-temperature high-pressure reaction kettle comprises a mechanical stirring device, is provided with a parameter panel for temperature, pressure and reaction time, is connected with a computer through a data line and can record the numerical values of all parameters, and the frequency is 13 s/time. The reaction kettle comprises an air inlet and an air outlet, the ball valve controls the switch, the air inlet can be filled with nitrogen/hydrogen, and the air outlet is connected with an emptying pipeline.
Hydrogenation experiment steps:
feeding: the reaction kettle was charged with 40g of benzyltoluene (abbreviated as MBT) and 5 wt.% -MBT of Ni-Mo/Al2O3Catalyst, mass 2 g;
pressure maintaining: installing a reaction kettle and a pipeline, maintaining the pressure of nitrogen (about 2-3MPa) in the reaction kettle for 30min, and regarding the pressure as no air leakage when the pressure is almost kept unchanged;
and (3) replacement: in order to ensure that the air in the kettle is exhausted, firstly purging for 3 times by using nitrogen (about 1-2MPa), then purging for 3 times by using hydrogen (about 1-2MPa), wherein the gauge pressure is 0MPa after the air is exhausted, and closing an inlet valve and an outlet valve;
heating: setting the reaction temperature to be 200 ℃, the stirring speed to be 1500rpm, starting to increase the furnace temperature, and entering a heating state;
reaction: when the temperature is kept at about 200 ℃, hydrogen (7-8MPa) is introduced to start the hydrogenation reaction, and the computer records the pressure drop and the time change.
And (4) ending: and when the pressure to be measured does not change any more, closing the heating, stirring and inlet and outlet valves, and stopping the reaction.
1) Hydrogenation effect of different catalysts:
the foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A hydrocatalytic material comprising a support and a catalyst, characterized in that the loading of the catalyst on the support is 5-12.5 wt.%, wherein the catalyst comprises nickel and molybdenum, and the mass ratio of nickel to molybdenum is (1-4): 1.
2. the hydrocatalytic material of claim 1, wherein said carrier is Al2O3A support or a zirconia support or a zeolite support.
3. The method of claim 1, comprising the steps of:
A. preparing a proper amount of molybdenum source solution, soaking the carrier with the molybdenum source solution, drying, and calcining in the air atmosphere to obtain a catalyst precursor I;
B. preparing a proper amount of nickel source solution, soaking the catalyst semi-finished product with the nickel source solution, drying, and calcining in an air atmosphere to obtain a catalyst precursor II;
C. and calcining the catalyst precursor II in a hydrogen atmosphere to obtain the catalyst.
4. The method of claim 3, wherein the molybdenum source solution in step A is a molybdate solution, and the solvent of the molybdate solution is ultrapure water or absolute ethyl alcohol.
5. The method of claim 3, wherein the nickel solution in step B is an aqueous solution of nickel nitrate or an ethanol solution, and the solvent of the solution is ultrapure water or absolute ethanol.
6. The method for preparing a hydrocatalytic material according to claim 3, wherein the drying in step A or step B is: drying at 80-120 deg.C for 18-36 h.
7. The method of claim 3, wherein the calcining in step A or step B is: calcining at the temperature of 400 ℃ for 4-6h under the air atmosphere.
8. The method of claim 3, wherein the hydrogen atmosphere in step C is 40-60mL/min in a tube furnace.
9. The method for preparing a hydrogenation catalyst material as claimed in claim 3, wherein the calcination in step C is performed at 550 ℃ for 4-6 h.
10. Use of a hydrogenation catalytic material according to any one of claims 1-2 for hydrogenation in liquid hydrogen storage.
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