CN113926462B - Hydrogenation catalytic material, preparation method and application - Google Patents
Hydrogenation catalytic material, preparation method and application Download PDFInfo
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- CN113926462B CN113926462B CN202111391419.0A CN202111391419A CN113926462B CN 113926462 B CN113926462 B CN 113926462B CN 202111391419 A CN202111391419 A CN 202111391419A CN 113926462 B CN113926462 B CN 113926462B
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 55
- 239000001257 hydrogen Substances 0.000 claims description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000003860 storage Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 16
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 238000010926 purge Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002474 experimental method Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052759 nickel Inorganic materials 0.000 abstract description 12
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 8
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 25
- 238000001354 calcination Methods 0.000 description 14
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- 239000005416 organic matter Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 230000035484 reaction time Effects 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
- 239000012018 catalyst precursor Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 239000000969 carrier Substances 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
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram 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
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-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
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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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
-
- 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 & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a hydrogenation catalytic material, a preparation method and application, wherein the catalyst comprises a carrier and a catalyst, the loading capacity of the catalyst on the carrier is 5-12.5wt.%, the catalyst comprises nickel element and 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 a non-noble metal material, so that the cost of the product is effectively reduced while the 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 an energy carrier which is clean and efficient, has rich resources and high energy density, can relieve the problems of shortage of traditional fossil energy reserves, environmental pollution, greenhouse effect and the like, and is of great importance to the sustainable development of human society.
The current common hydrogen energy storage modes comprise three modes of liquid hydrogen storage, high-pressure gas 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 and is easy to generate hydrogen embrittlement phenomenon, and has potential danger; the low-temperature liquid hydrogen storage needs a liquefied storage tank with excellent heat insulation performance, and has strict requirements on materials; solid hydrogen storage has larger volume storage capacity, but the hydrogen storage material can deteriorate, and phenomena such as hydrogen damage, hydrogen corrosion and the like are generated, so that the recycling of the hydrogen carrier is influenced. The technology of liquid-phase organic matter hydrogen storage is studied in the 80 s of the 20 th century, and the technology utilizes unsaturated bonds in organic matters to realize the storage and release of hydrogen. Compared with the above hydrogen storage modes, the hydrogen carrier used for liquid-phase organic matter hydrogen storage can utilize the existing oil transportation equipment because of the similar property to gasoline, and has larger mass hydrogen storage density (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, etc.) has stable physical and chemical properties, can be recycled, and has a service life of about 20 years.
The catalyst for adding and dehydrogenating the liquid-phase organic matter hydrogen storage technology is generally Ru/Pt loaded on Al 2O3、TiO2、SiO2, molecular sieve, active 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 of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a hydrogenation catalytic material, a preparation method and application, and the catalyst material matched with nickel/molybdenum non-noble metal is adopted, so that the cost of the catalyst is effectively reduced, and meanwhile, the catalytic performance is fully improved.
To achieve the above object, embodiments of the present invention provide a hydrogenation catalytic material comprising a support and a catalyst, the catalyst having a loading of 5 to 12.5wt.% on the support, wherein the catalyst comprises nickel element and molybdenum element, and the mass ratio of nickel element to molybdenum element is (1 to 4): 1.
In one or more embodiments of the invention, the support is an Al 2O3 support or a zirconia support or a zeolite support.
In one or more embodiments of the present invention, a method for preparing a hydrogenation catalytic material includes the steps of: A. preparing a proper amount of molybdenum source solution, soaking a carrier in the molybdenum source solution, drying, and calcining in an air atmosphere to obtain a catalyst precursor I; B. preparing a proper amount of nickel source solution, soaking a catalyst semi-finished product with the nickel source solution, drying, and calcining in an air atmosphere to obtain a catalyst precursor II; C. calcining the second catalyst precursor 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 ethanol.
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 80-120deg.C for 18-36 hr.
In one or more embodiments of the invention, the calcination in step a or step B is either: calcining at 300-400 deg.C for 4-6 hr in 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 invention, the calcination in step C is performed at 500-550℃for 4-6h.
In one or more embodiments of the invention, the hydrogenation catalytic material as described previously is used in the hydrogenation of liquid hydrogen storage.
In one or more embodiments of the present invention, the hydrogenation is applied specifically as follows: the dosage of the catalyst is controlled to be 5-10% of the mass of the carrier; evacuating a qualified reaction device (such as a reaction device which passes through pressure maintaining air tightness test in advance); the reaction is carried out under the conditions of heating and stirring until the reaction is terminated. Preferably, the reaction is terminated by monitoring the pressure drop across the reaction apparatus during the course of the reaction, and the reaction is terminated as the pressure state stabilizes (no longer decreases). Preferably, the reaction temperature is 180-200 ℃. Preferably, the stirring speed is 1300-1500rpm.
Compared with the prior art, the hydrogenation catalytic material, the preparation method and the application according to the embodiment of the invention have the following advantages:
the existing catalyst is loaded by noble metal and has high price, and the catalyst in the patent adopts Ni and Mo non-noble metal loaded alumina, so that the economic cost is saved;
The beneficial effects are that:
The preparation cost of the catalyst is reduced, the cost of the noble metal catalyst is high, and Ni and Mo used in the experiment are non-noble metal catalysts, but in the hydrogenation time, compared with the noble metal catalyst, the catalyst has better catalytic performance;
The alumina carrier has good adaptability, alumina carriers with different pore sizes can be selected according to the reaction requirement, the price is low, and the synthesis cost and the economic cost are saved;
The catalyst is Ni and Mo bimetal, and the catalyst plays a role in synergy, thereby promoting the improvement of hydrogenation efficiency.
Drawings
FIG. 1 is a graph of pressure versus time for different proportions of catalyst according to an embodiment of the invention;
FIG. 2 is an XRD pattern for different proportions of catalyst according to an embodiment of the invention;
fig. 3 is a GC-MS diagram of a hydrogen carrier, benzyltoluene, after hydrogenation according to an embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
Example 1
As shown in fig. 1 to 3, the hydrogenation catalyst material according to the preferred embodiment of the present invention:
The hydrogen carrier (liquid organic matter) is benzyl toluene, and the hydrogenation catalytic material is Ni-Mo/Al 2O3.
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) Preparing by adopting an isovolumetric impregnation method, and impregnating the solution A into an Al 2O3 carrier to obtain a precursor B;
3) Placing the precursor B in an oven, and drying at 100 ℃ for 24 hours to obtain a dried product C;
4) Calcining the product C in a muffle furnace in an air atmosphere at 350 ℃ for 4 hours to obtain a product D;
5) Preparing nickel nitrate solution with a certain concentration, wherein the solvent is ultrapure water to obtain solution E;
6) And similarly, repeating the steps 2), 3) and 4) to load Ni on the product D to obtain a product F;
7) And placing the product F in a tubular furnace, calcining for 4 hours at 500 ℃ under the hydrogen atmosphere with the flow of 40-60mL/min, and obtaining the catalyst named as Ni-Mo/Al 2O3.
Hydrogenation test conditions:
Hydrogenation equipment: the high-temperature high-pressure reaction kettle comprises a mechanical stirring device, is provided with a parameter panel of temperature, pressure and reaction time, and can record the numerical value of each parameter by being connected with a computer through a data line, wherein 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 vessel was charged with 40g of benzyltoluene (abbreviated as MBT) and 5wt.% of Ni-Mo/Al 2O3 catalyst (referred to as catalyst 5% by mass of MBT), 2g by mass;
pressure maintaining: installing a reaction kettle and a pipeline, and maintaining the pressure of nitrogen (about 2-3 MPa) in the reaction kettle for 30min, wherein the pressure is almost unchanged and is regarded as airtight;
replacement: in order to ensure that the air in the kettle is exhausted, nitrogen (about 1-2 MPa) is firstly used for purging 3 times, then hydrogen (about 1-2 MPa) is used for purging 3 times, the gauge pressure is 0MPa after the air is exhausted, and the inlet and outlet valves are closed;
heating: setting the reaction temperature to 200 ℃, stirring at 1500rpm, and starting to increase the furnace temperature to enter a heating state;
The reaction: when the temperature is maintained at about 200 ℃, hydrogen (7-8 MPa) is introduced to start hydrogenation reaction, and the pressure drop and time change are recorded by a computer.
Ending: and when the pressure to be measured is not changed any more, the heating, stirring and inlet and outlet valves are closed, and the reaction is stopped.
1) Hydrogenation effect of catalysts in different proportions:
2) After the hydrogenation reaction is completed by using 7.5% Ni-2.5% Mo/Al 2O3 catalyst, the GC-MS peak and product ratio of the hydrogenated benzyltoluene as hydrogen carrier are shown in figure 3 (only one proportion is selected for illustration in this example because the catalysts of the four proportions are completely hydrogenated), wherein the benzylbenzene is a trace impurity contained in the benzyltoluene as raw material, and the hydrogenation is also complete.
Example 2
Hydrogenation catalytic 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) Preparing by adopting an isovolumetric impregnation method, and impregnating the solution A into a zirconia carrier to obtain a precursor B;
3) Placing the precursor B in an oven, and drying at 80 ℃ for 18 hours to obtain a dried product C;
4) Calcining the product C in a muffle furnace in an air atmosphere at 400 ℃ for 5 hours to obtain a product D;
5) Preparing nickel nitrate solution with a certain concentration, wherein the solvent is ultrapure water to obtain solution E;
6) And similarly, repeating the steps 2), 3) and 4) to load Ni on the product D to obtain a product F;
7) And placing the product F in a tubular furnace, calcining for 4 hours at 500 ℃ under the hydrogen atmosphere with the flow of 40-60mL/min, and obtaining 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 of temperature, pressure and reaction time, and can record the numerical value of each parameter by being connected with a computer through a data line, wherein 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 vessel was charged with 40g of benzyltoluene (abbreviated MBT) and 7.5wt.% of a Ni-Mo/zirconia catalyst of MBT, 3g in mass;
pressure maintaining: installing a reaction kettle and a pipeline, and maintaining the pressure of nitrogen (about 2-3 MPa) in the reaction kettle for 30min, wherein the pressure is almost unchanged and is regarded as airtight;
Replacement: in order to ensure that the air in the kettle is exhausted, nitrogen (about 1-2 MPa) is firstly used for purging 3 times, then hydrogen (about 1-2 MPa) is used for purging 3 times, the gauge pressure is 0MPa after the air is exhausted, and the inlet and outlet valves are closed;
heating: setting the reaction temperature to 180 ℃, stirring at 1400rpm, and starting to raise the furnace temperature to enter a heating state;
the reaction: when the temperature is maintained at about 180 ℃, hydrogen (7-8 MPa) is introduced to start hydrogenation reaction, and the pressure drop and time change are recorded by a computer.
Ending: and when the pressure to be measured is not changed any more, the heating, stirring and inlet and outlet valves are closed, and the reaction is stopped.
1) Hydrogenation effect of catalysts in different proportions:
Example 3
Hydrogenation catalytic material according to preferred embodiments of the present invention
The hydrogen carrier (liquid organic matter) is benzyl toluene, and the hydrogenation catalytic material is Ni-Mo/Al 2O3.
Preparing a hydrogenation catalytic material:
1) Preparing a potassium molybdate solution with a certain concentration, wherein the solvent is absolute ethyl alcohol, so as to obtain a solution A;
2) Preparing by adopting an isovolumetric impregnation method, and impregnating the solution A into a zeolite carrier to obtain a precursor B;
3) Placing the precursor B in an oven, and drying at 120 ℃ for 36 hours to obtain a dried product C;
4) Calcining the product C in a muffle furnace in an air atmosphere at 300 ℃ for 6 hours to obtain a product D;
5) Preparing nickel nitrate solution with a certain concentration, wherein the solvent is absolute ethyl alcohol, so as to obtain solution E;
6) And similarly, repeating the steps 2), 3) and 4) to load Ni on the product D to obtain a product F;
7) And placing the product F in a tubular furnace, calcining for 4 hours at 500 ℃ under the hydrogen atmosphere with the flow of 40-60mL/min, and obtaining the catalyst named as Ni-Mo/Al 2O3.
Hydrogenation test conditions:
Hydrogenation equipment: the high-temperature high-pressure reaction kettle comprises a mechanical stirring device, is provided with a parameter panel of temperature, pressure and reaction time, and can record the numerical value of each parameter by being connected with a computer through a data line, wherein 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 vessel was charged with 40g of benzyltoluene (abbreviated MBT) and 10wt.% of a Ni-Mo/zeolite catalyst of MBT, mass 4g;
pressure maintaining: installing a reaction kettle and a pipeline, and maintaining the pressure of nitrogen (about 2-3 MPa) in the reaction kettle for 30min, wherein the pressure is almost unchanged and is regarded as airtight;
Replacement: in order to ensure that the air in the kettle is exhausted, nitrogen (about 1-2 MPa) is firstly used for purging 3 times, then hydrogen (about 1-2 MPa) is used for purging 3 times, the gauge pressure is 0MPa after the air is exhausted, and the inlet and outlet valves are closed;
heating: setting the reaction temperature to 190 ℃, stirring at 1300rpm, and starting to increase the furnace temperature to enter a heating state;
the reaction: when the temperature is maintained at about 190 ℃, hydrogen (7-8 MPa) is introduced to start hydrogenation reaction, and the pressure drop and time change are recorded by a computer.
Ending: and when the pressure to be measured is not changed any more, the heating, stirring and inlet and outlet valves are closed, and the reaction is stopped.
1) Hydrogenation effect of catalysts in different proportions:
| Sequence number | Catalyst | Hydrogenation time/min |
| Sample 1 | 2.5% Ni-2.5% Mo/zeolite | 39.0 |
| Sample 2 | 5.0% Ni-2.5% Mo/zeolite | 35.5 |
| Sample 3 | 7.5% Ni-2.5% Mo/zeolite | 29.0 |
| Sample 4 | 10.0% Ni-2.5% Mo/zeolite | 32.0 |
| Sample 5 | 7.5% Ni/zeolite | 50.0 |
| Sample 6 | 2.5% Mo/zeolite | Infinity of infinity |
Example 4
Hydrogenation catalytic material according to a preferred embodiment of the present invention:
The hydrogen carrier (liquid organic matter) is benzyl toluene, and the hydrogenation catalytic material is Ni-Mo/Al 2O3.
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) The preparation method comprises the steps of (1) preparing the precursor by adopting an isovolumetric impregnation method, and impregnating the solution A into an Al 2O3 carrier (adopting Al 2O3 carriers with different specifications for different samples according to the following table) to obtain a precursor B;
3) Placing the precursor B in an oven, and drying at 100 ℃ for 24 hours to obtain a dried product C;
4) Calcining the product C in a muffle furnace in an air atmosphere at 350 ℃ for 4 hours to obtain a product D;
5) Preparing nickel nitrate solution with a certain concentration, wherein the solvent is ultrapure water or absolute ethyl alcohol to obtain solution E;
6) And similarly, repeating the steps 2), 3) and 4) to load Ni on the product D to obtain a product F;
7) And placing the product F in a tubular furnace, calcining for 4 hours at 500 ℃ under the hydrogen atmosphere with the flow of 40-60mL/min, and obtaining the catalyst named as Ni-Mo/Al 2O3.
Hydrogenation test conditions:
Hydrogenation equipment: the high-temperature high-pressure reaction kettle comprises a mechanical stirring device, is provided with a parameter panel of temperature, pressure and reaction time, and can record the numerical value of each parameter by being connected with a computer through a data line, wherein 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 is filled with 40g of benzyl toluene (abbreviated as MBT) and 5wt.% of Ni-Mo/Al 2O3 catalyst of MBT, and the mass is 2g;
pressure maintaining: installing a reaction kettle and a pipeline, and maintaining the pressure of nitrogen (about 2-3 MPa) in the reaction kettle for 30min, wherein the pressure is almost unchanged and is regarded as airtight;
Replacement: in order to ensure that the air in the kettle is exhausted, nitrogen (about 1-2 MPa) is firstly used for purging 3 times, then hydrogen (about 1-2 MPa) is used for purging 3 times, the gauge pressure is 0MPa after the air is exhausted, and the inlet and outlet valves are closed;
heating: setting the reaction temperature to 200 ℃, stirring at 1500rpm, and starting to increase the furnace temperature to enter a heating state;
The reaction: when the temperature is maintained at about 200 ℃, hydrogen (7-8 MPa) is introduced to start hydrogenation reaction, and the pressure drop and time change are recorded by a computer.
Ending: and when the pressure to be measured is not changed any more, the heating, stirring and inlet and outlet valves are closed, and the reaction is stopped.
1) Hydrogenation effect of different catalysts:
The foregoing descriptions of specific exemplary embodiments of the present invention are 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 the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various 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 (1)
1. The application of the hydrogenation catalytic material in the liquid hydrogen storage is characterized in that the hydrogenation catalytic material is 7.5 percent Ni-2.5 percent Mo/Al 2O3, wherein the pore diameter of the carrier alumina is 3.6343nm, the specific surface area is 343.3524m 2/g, the hydrogen carrier of the liquid hydrogen storage is benzyl toluene,
The hydrogenation experiment steps are as follows:
Feeding: 40g of benzyl toluene and 7.5 percent of Ni-2.5 percent of Mo/Al 2O3 catalyst accounting for 5 percent of the mass of the benzyl toluene are filled in a reaction kettle, and the mass is 2g;
Pressure maintaining: installing a reaction kettle and a pipeline, and maintaining the pressure for 30min under 2-3MPa of nitrogen in the reaction kettle, wherein the pressure is almost unchanged and is regarded as airtight;
Replacement: in order to ensure that the air in the kettle is exhausted, 1-2MPa nitrogen is firstly used for purging 3 times, then 1-2MPa hydrogen is used for purging 3 times, the gauge pressure is 0MPa after the air is exhausted, and the inlet and outlet valves are closed;
heating: setting the reaction temperature to 200 ℃, stirring at 1500rpm, and starting to increase the furnace temperature to enter a heating state;
The reaction: when the temperature is maintained at 200 ℃, 7-8MPa of hydrogen is introduced to start hydrogenation reaction, and the pressure drop and time change are recorded by a computer;
ending: and when the pressure to be measured is not changed any more, the heating, stirring and inlet and outlet valves are closed, and the reaction is stopped.
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