CN114804020B - Slurry hydrogen storage material and preparation method thereof - Google Patents
Slurry hydrogen storage material and preparation method thereof Download PDFInfo
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- CN114804020B CN114804020B CN202210565846.4A CN202210565846A CN114804020B CN 114804020 B CN114804020 B CN 114804020B CN 202210565846 A CN202210565846 A CN 202210565846A CN 114804020 B CN114804020 B CN 114804020B
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 256
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 256
- 239000001257 hydrogen Substances 0.000 title claims abstract description 256
- 239000011232 storage material Substances 0.000 title claims abstract description 52
- 239000002002 slurry Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 32
- 150000004678 hydrides Chemical class 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 claims description 25
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical group [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical compound C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- FUUPYXUBNPJSOA-UHFFFAOYSA-N 9-ethyl-1,2,3,4,4a,4b,5,6,7,8,8a,9a-dodecahydrocarbazole Chemical compound C12CCCCC2N(CC)C2C1CCCC2 FUUPYXUBNPJSOA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 abstract description 27
- 239000007791 liquid phase Substances 0.000 abstract description 8
- 235000011837 pasties Nutrition 0.000 abstract description 4
- 230000005923 long-lasting effect Effects 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 42
- 238000003795 desorption Methods 0.000 description 36
- 238000010438 heat treatment Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 11
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 10
- 229910020828 NaAlH4 Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000969 carrier Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012546 transfer 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
- -1 and meanwhile Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010952 in-situ formation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- JNNCNNLHVBNIMH-UHFFFAOYSA-N n,n-dimethyl-1-phenylhex-5-en-1-yn-3-amine Chemical compound C=CCC(N(C)C)C#CC1=CC=CC=C1 JNNCNNLHVBNIMH-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
Classifications
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- 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
- C01B3/0073—Slurries, Suspensions
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a pasty hydrogen storage material and a preparation method thereof. The slurry hydrogen storage material is prepared by mixing a hydrogen-rich liquid organic hydrogen carrier LOHC, a solid hydride NaAlH 4, a Ni-based catalyst precursor, a Ti-based catalyst precursor and a catalyst carrier. According to the invention, the liquid-phase organic hydrogen carrier (LOHC) and the solid hydride hydrogen storage material NaAlH 4 are compounded to prepare the novel slurry hydrogen storage material for the first time, and the hydrogen storage amount of the novel slurry hydrogen storage material and the hydrogen storage temperature of the novel slurry hydrogen storage material are relatively high, and the hydrogen storage temperature is close to the hydrogen storage temperature, so that the high hydrogen storage amount (more than 5.0 wt%), the relatively low operation temperature (less than 200 ℃) and relatively fast hydrogen storage dynamics are ensured, the long-lasting and short-term prevention of the liquid-phase organic hydrogen carrier LOHC and the solid hydride NaAlH 4 are realized, and the novel slurry hydrogen storage material is a hydrogen storage material with a very good application prospect.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a pasty hydrogen storage material and a preparation method thereof.
Background
The advantages of clean and pollution-free hydrogen energy, high heat value and the like make the hydrogen energy expected in the last decades, and the hydrogen energy is considered as an indispensable part of solving the energy problem and developing low-carbon economy by a plurality of people. Although hydrogen energy is being developed vigorously, the key problems in three aspects of hydrogen production, hydrogen storage and fuel cells are not well solved. Particularly, the hydrogen storage mode which is used as a bridge between the preparation and the application of the hydrogen and can be widely applied does not exist. The existing vehicle-mounted hydrogen storage mode is also a mode of storing hydrogen by utilizing a physical high-pressure hydrogen storage tank, and has a plurality of defects in the aspects of energy efficiency, volume hydrogen storage quantity, safety and the like. Therefore, the lack of efficient hydrogen storage materials can be said to be a bottleneck in the development of hydrogen energy.
At present, liquid Organic Hydrogen Carriers (LOHC) and solid hydrides are two types of hydrogen storage materials that are considered to be possible to solve the problem of hydrogen storage, but the main disadvantage of liquid organic hydrogen carriers is poor kinetics of hydrogen absorption and desorption, while the main disadvantage of solid hydrides is that materials with high hydrogen storage volumes generally have high temperature of hydrogen absorption and desorption, and difficult management of heat conduction and volume changes. In this regard, researchers have proposed that the two types of hydrogen storage materials are combined to form a slurry-like hydrogen storage material, and it is possible to make a long-term use against short-term use and obtain a hydrogen storage material having more excellent performance. For example, patent application CN 1380136A of university of Zhejiang in 2002 proposes a slurry hydrogen storage material, and a liquid phase organic hydrogen carrier such as benzene, toluene, naphthalene, etc. can be added into a solid hydride hydrogen storage material to form a slurry with solid-liquid mixture, so that the problems of heat transfer and volume change of the solid hydride can be effectively solved, however, because the selected liquid phase organic hydrogen carrier has very high hydrogen release temperature and poor dynamics, they only consider the hydrogen absorption process, namely the high-efficiency hydrogen storage material with 6.5 wt% of hydrogen storage amount, in fact, hydrogen can only be absorbed very slowly, but the hydrogen release speed is slower, and the practical value is not high.
The group of subject has proposed a patent application (CN 111013593A) showing: n-doped aromatic compound liquid organic hydrogen carriers such as N-ethylcarbazole, 2-methylindole, 1-methylindole and the like can realize faster hydrogen absorption and desorption at the temperature of below 200 ℃ under the catalysis of an in-situ generated Ni-based catalyst. However, how to solve the problems of slow absorption and desorption kinetics of the liquid organic hydrogen carrier, difficult heat transfer of the solid hydride hydrogen storage material and volume change in the absorption and desorption process under the conditions of ensuring high hydrogen storage amount (more than 5.0 wt%), lower operation temperature (less than 200 ℃) and quicker absorption and desorption kinetics is a new research direction provided by the subject group, and is also a technical bottleneck which needs to be overcome in the prior art of the hydrogen storage material.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims to provide a pasty hydrogen storage material, which is a novel pasty hydrogen storage material based on the combination of liquid organic hydrogen carriers LOHC such as N-ethyl carbazole, methylindole and the like and solid hydride NaAlH 4.
Another object of the present invention is to provide a method for preparing a slurry hydrogen storage material.
The technical scheme adopted for realizing the purpose of the invention is as follows: the slurry hydrogen storage material is prepared by mixing a hydrogen-rich liquid organic hydrogen carrier LOHC, a solid hydride NaAlH 4, a Ni-based catalyst precursor, a Ti-based catalyst precursor and a catalyst carrier.
Preferably, the hydrogen-rich liquid organic hydrogen carrier LOHC is selected from one of dodecahydro N-ethylcarbazole H 12 -NEC, octahydro 2-methylindole H 8 -2-MID or octahydro 1-methylindole H 8 -1-MID.
Preferably, the Ni-based catalyst precursor is bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2, and the Ti-based catalyst precursor is tetrabutyl titanate Ti (OBu) 4.
Preferably, the catalyst carrier is selected from one of Al 2O3、SiO2 or graphene.
Preferably, the molar ratio of the hydrogen-rich liquid organic hydrogen carrier LOHC, the solid hydride NaAlH 4、Ni(COD)2 and the Ti (OBu) 4 is 1: (0.1 to 1): (0.005-0.01): (0.005-0.01).
Preferably, the dosage of the catalyst carrier is 2.5-5 wt% of the total mass of the hydrogen-rich liquid organic hydrogen carrier LOHC, the solid hydride NaAlH 4, the Ni-based catalyst precursor and the Ti-based catalyst precursor.
Preferably, the hydrogen-rich liquid organic hydrogen carrier LOHC is obtained by catalyzing LOHC hydrogenation in a high-pressure reaction kettle by using a Ru/Al 2O3 catalyst.
The technical scheme adopted for realizing the other purpose of the invention is as follows: the preparation method of the slurry hydrogen storage material comprises the following preparation steps:
1) Preparation of hydrogen-rich liquid organic hydrogen carrier LOHC
In a high-pressure reaction kettle, catalyzing LOHC by using a Ru/Al 2O3 catalyst to hydrogenate to obtain LOHC in a hydrogen-rich state;
2) Preparation of slurry hydrogen storage material
And (3) mixing the hydrogen-rich LOHC, the solid hydride NaAlH 4, the Ni-based catalyst precursor and the Ti-based catalyst precursor prepared in the step (1) in an inert atmosphere in proportion, adding a catalyst carrier, and placing in a high-pressure reaction kettle to be uniformly mixed.
Wherein the hydrogen-rich liquid organic hydrogen carrier LOHC is selected from one of dodecahydro N-ethylcarbazole H 12 -NEC, octahydro 2-methylindole H 8 -2-MID or octahydro 1-methylindole H 8 -1-MID; the Ni-based catalyst precursor is bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2, and the Ti-based catalyst precursor is tetrabutyl titanate Ti (OBu) 4; the catalyst carrier is selected from one of Al 2O3、SiO2 or graphene.
Wherein, the molar ratio of the LOHC in the hydrogen-rich state, the solid hydride NaAlH 4, the Ni-based catalyst precursor bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2 and the Ti-based catalyst precursor tetrabutyl titanate Ti (OBu) 4 is 1: (0.1 to 1): (0.005-0.01): (0.005-0.01); the dosage of the catalyst carrier is 2.5-5wt% of the sum of the total mass of hydrogen-rich LOHC, solid hydride NaAlH 4, ni-based catalyst precursor bis- (1, 5-cyclooctadiene) Ni (COD) 2 and Ti-based catalyst precursor tetrabutyl titanate Ti (OBu) 4.
Compared with the prior art, the invention has the following technical advantages:
(1) According to the invention, the liquid-phase organic hydrogen carrier (LOHC) and the solid hydride hydrogen storage material NaAlH 4 are compounded to prepare the novel slurry hydrogen storage material for the first time, and the hydrogen storage amount of the novel slurry hydrogen storage material and the hydrogen storage temperature of the novel slurry hydrogen storage material are relatively high, and the hydrogen storage temperature is close to the hydrogen storage temperature, so that the high hydrogen storage amount (more than 5.0 wt%), the relatively low operation temperature (less than 200 ℃) and relatively fast hydrogen storage dynamics are ensured, the long-lasting and short-term prevention of the liquid-phase organic hydrogen carrier LOHC and the solid hydride NaAlH 4 are realized, and the novel slurry hydrogen storage material is a hydrogen storage material with a very good application prospect.
(2) The invention prepares a novel slurry hydrogen storage material based on N-ethylcarbazole (NEC), 2-methylindole (2-MID), 1-methylindole (1-MID) and solid hydride hydrogen storage material NaAlH 4 with high hydrogen storage capacity and lower operation temperature, and in order to ensure rapid hydrogen absorption and desorption kinetics, ti-based catalyst precursor tetrabutyl titanate Ti (OBu) 4 and Ni-based catalyst precursor bis- (1, 5-cyclooctadiene) nickel are introduced into the material to be used as a hydrogen absorption and desorption catalyst of the solid hydride hydrogen storage material NaAlH 4 and a liquid-phase organic hydrogen carrier LOHC in an in-situ formation mode, and NaAlH 4 can be used as a cocatalyst of the liquid-phase organic hydrogen carrier LOHC, and can reduce the hydrogen absorption and desorption temperature of the LOHC through reactive coupling.
Drawings
FIG. 1 is a graph showing the change of the hydrogen absorption and desorption kinetics measured in example 1 of the present invention.
FIG. 2 is a diagram of an apparatus for testing hydrogen absorption and desorption kinetics curves in accordance with the present invention.
FIG. 3 is a graph showing the capacity change of the cyclic hydrogen absorption and desorption according to example 2 of the present invention.
Detailed Description
The invention is further described below with reference to examples.
The invention relates to a slurry hydrogen storage material, which is prepared by mixing a hydrogen-rich liquid organic hydrogen carrier LOHC, a solid hydride NaAlH 4, a Ni-based catalyst precursor, a Ti-based catalyst precursor and a catalyst carrier, and specifically comprises the following preparation steps:
1) Preparation of hydrogen-rich liquid organic hydrogen carrier LOHC
In a high-pressure reaction kettle, catalyzing LOHC hydrogenation by using a Ru/Al 2O3 catalyst to obtain hydrogen-rich LOHC (preferably one of dodecahydro N-ethyl carbazole H 12 -NEC, octahydro 2-methylindole H 8 -2-MID and octahydro 1-methylindole H 8 -1-MID) and separating by centrifugation.
2) Preparation of slurry hydrogen storage material
Mixing the LOHC in the hydrogen-rich state, the solid hydride NaAlH 4, the Ni-based catalyst precursor and the Ti-based catalyst precursor prepared in the step 1) in proportion in an inert atmosphere, adding a catalyst carrier (preferably one of Al 2O3、SiO2 or graphene), and uniformly mixing in a high-pressure reaction kettle.
Wherein, the molar ratio of the hydrogen-rich LOHC to the solid hydride hydrogen storage material NaAlH 4 to the Ni-based catalyst precursor to the Ti-based catalyst precursor is 1: (0.1 to 1): (0.005-0.01): (0.005-0.01); the dosage of the catalyst carrier is 2.5-5wt% of the sum of the total mass of hydrogen-rich LOHC, solid hydride NaAlH 4, ni-based catalyst precursor bis- (1, 5-cyclooctadiene) Ni (COD) 2 and Ti-based catalyst precursor tetrabutyl titanate Ti (OBu) 4.
The invention relates to a method for testing the hydrogen absorption and desorption of a slurry hydrogen storage material, which comprises the following steps:
In the preparation process of the slurry hydrogen storage material, stirring and mixing uniformly in a high-pressure reaction kettle by using a magnet, continuously maintaining a stirring state, vacuumizing and detecting leakage, heating to 80 ℃, preserving heat by 2h, introducing 0.1 to MPa H 2, heating to 130-200 ℃ immediately, and measuring the generated gas condition by using a mass flowmeter with a one-way valve to obtain a hydrogen release curve. After hydrogen is not produced any more, cooling to 120-180 ℃, filling 5-10 MPa H 2 after the temperature is stable, and measuring the pressure change by using a pressure sensor to obtain a hydrogen absorption curve. Cooling to room temperature after no hydrogen absorption, vacuumizing, then introducing 0.1 MPa H 2, immediately heating to 130-200 ℃, measuring the generated gas condition by using a mass flowmeter with a one-way valve, and repeating the steps, thereby measuring the cyclic hydrogen absorption and desorption performance. The apparatus for testing the hydrogen absorption and desorption kinetics curves is shown in fig. 2.
Under the reaction condition of the reaction temperature of 80 ℃ and the heat preservation of 2 h, ni (COD) 2 and Ti (OBu) 4 can be reduced into a Ni/Ti composite catalyst (nano-Ni/Ti@ carrier catalyst), wherein NaAlH 4 also plays a role of a reducing agent, and meanwhile, catalyst carriers such as LOHC and Al 2O3 in a hydrogen-rich state play a role of preventing Ni and Ti from agglomerating into larger particles. It should be noted that, the present invention introduces the hydrogen absorbing and releasing catalyst nano-Ni/Ti@ carrier catalyst into the slurry hydrogen storage material through the in-situ formation mode for the first time, and is a non-noble metal catalyst.
The hydrogen absorption and desorption reaction process of the slurry hydrogen storage material containing the LOHC in a hydrogen-rich state and the NaAlH 4 as a solid hydride hydrogen storage material is as follows:
The hydrogen release reaction process is as follows: h n-LOHC + NaAlH4 → LOHC + NaH + Al + H2;
The hydrogen absorption reaction process is as follows: lohc+nah+al+h 2 → Hn-LOHC + NaAlH4;
Example 1
In a high-pressure reaction kettle, catalyzing N-ethylcarbazole (NEC) to hydrogenate by using Ru/Al 2O3 catalyst to obtain H 12 -NEC in a hydrogen-rich state, and separating by centrifugation.
H 12-NEC、NaAlH4、Ni(COD)2、Ti(OBu)4 in the hydrogen-rich state was reacted under an inert atmosphere according to 1:1:0.01: mixing at a molar ratio of 0.01 (2.07 g:0.54 g:0.028 g:0.034 g), adding graphene (0.067 and g) accounting for 2.5-wt% of the total mass of the substances, placing the mixture into a high-pressure reaction kettle, stirring and mixing the mixture uniformly by using a magnet, keeping a stirring state all the time, vacuumizing and detecting leakage, heating to 80 ℃, preserving heat for reaction 2h, introducing 0.1 MPa H 2, heating to 200 ℃ immediately, and measuring the generated gas condition by using a mass flowmeter with a one-way valve to obtain a hydrogen release curve. And after no more hydrogen is produced, cooling to 180 ℃, filling 10 MPa H 2 after the temperature is stable, and measuring the pressure change by using a pressure sensor to obtain a hydrogen absorption curve. As a result, as shown in FIG. 1, the hydrogen desorption reaction was able to release hydrogen by 10h to approximately 5.5 wt% (hydrogen yield to approximately 100%) at 200℃and 0.1 MPa H 2, and the corresponding hydrogen desorption reaction was able to absorb hydrogen by 10h exceeding 5.4 wt% at 180℃and 10 MPa H 2. The hydrogen absorption and desorption processes have a few stages with different rates, probably because H 12 -NEC and NaAlH 4 have multi-step hydrogen absorption and desorption processes, and the dynamics of different processes are different. The hydrogen absorption and desorption processes are as follows:
6NaAlH4 = 2Na3AlH6 + 4Al + 6H2；
2Na3AlH6 = 6NaH + 2Al + 3H2；
C14H25N = C14H21N + 2H2；
C14H21N = C14H17N + 2H2；
C14H17N = C14H13N + 2H2。
Example 2
In a high-pressure reaction kettle, catalyzing 2-methylindole (2-MID) to hydrogenate by using a Ru/Al 2O3 catalyst to obtain H 8 -2-MID in a hydrogen-rich state, and centrifugally separating.
H 8-2-MID、NaAlH4、Ni(COD)2、Ti(OBu)4 in the hydrogen-rich state was reacted under an inert atmosphere according to 1:0.1:0.005: mixing at a molar ratio of 0.005 (6.96 g:0.27 g:0.069 g:0.085 g), adding gamma-Al 2O3 (0.40 g) with particle size of 20 nm, which is 5-wt% of the total mass of the materials, placing the materials in a high-pressure reaction kettle, stirring and mixing uniformly by using a magnet, keeping a stirring state all the time, vacuumizing and detecting leakage, heating to 80 ℃, preserving heat for reaction 2 h, introducing 0.1 MPa H 2, heating to 200 ℃ immediately, and measuring the generated gas condition by using a mass flowmeter with a one-way valve to obtain a hydrogen release curve. After no more hydrogen is produced, the temperature is reduced to 180 ℃,5 MPa H 2 is filled after the temperature is stable, and a pressure sensor is used for measuring the pressure change to obtain a hydrogen absorption curve. Cooling to room temperature after no hydrogen absorption, vacuumizing, then introducing 0.1 MPa H 2, immediately heating to 200 ℃, measuring the generated gas condition by using a mass flowmeter with a one-way valve, and repeating the steps, thereby measuring the cyclic hydrogen absorption and desorption performance. The results show that: the hydrogen release energy is basically completed at 4 h, the hydrogen absorption energy is completed within 2 h, the hydrogen storage capacity is only slightly attenuated after 5 times of hydrogen absorption and release, and the capacity change of cyclic hydrogen absorption and release is shown in fig. 3. The amount of first hydrogen absorption and desorption exceeds 5.9 wt% and exceeds the expected theoretical hydrogen storage amount of 5.8: 5.8 wt%, probably because of the reaction between NaAlH 4 and active hydrogen on H 8 -2-MID in a hydrogen-rich state (H on N-H bond), namely the reaction process is as follows:
10+ NaAlH4 = + 7 + NaH + 43H2
This indicates that certain reaction coupling exists between the hydrogen absorption and desorption reactions of LOHC and NaAlH 4, and the reaction can be promoted mutually. With the same charge as this example, the hydrogen desorption conditions were changed to 130 ℃ and 0.1 MPa H 2, the hydrogen desorption conditions were changed to 130 ℃, the hydrogen desorption amount measured by 10 MPa H 2 and 10 h was 5.1 wt%, and the hydrogen desorption amount measured by 6 h was 5.0 wt%, thus realizing a slurry hydrogen storage system with reversible hydrogen desorption exceeding 5.0 wt% at 130 ℃ for the first time.
Example 3
In a high-pressure reaction kettle, catalyzing 1-MID hydrogenation by using Ru/Al 2O3 catalyst to obtain H 8 -1-MID in a hydrogen-rich state, and separating by centrifugation.
H 8-1-MID、NaAlH4、Ni(COD)2、Ti(OBu)4 in the hydrogen-rich state was reacted under an inert atmosphere according to 1:0.1:0.005: mixing with molar ratio (6.96 g:0.27 g:0.069 g:0.085 g) of 0.005, adding nano SiO 2 (0.295 g) accounting for 4 wt% of the total mass of the substances, placing the mixture into a high-pressure reaction kettle, stirring and mixing uniformly by using a magnet, keeping stirring state all the time, vacuumizing and detecting leakage, heating to 80 ℃, preserving heat for reaction 2h, introducing 0.1 MPa H 2, heating to 180 ℃ immediately, and measuring the generated gas condition by using a mass flowmeter with a one-way valve to obtain a hydrogen release curve. After no more hydrogen is produced, the temperature is reduced to 150 ℃,7 MPa H 2 is filled after the temperature is stable, and a pressure sensor is used for measuring the pressure change to obtain a hydrogen absorption curve. The results show that: the hydrogen release can be basically completed at 8 h (5.3 wt percent of hydrogen release), the hydrogen absorption can be completed in 3 h (5.1 wt percent of hydrogen absorption), and the total reaction process is as follows:
20 + 2NaAlH4 = 20 + 2NaH + 2Al + 83H2。
Comparative example 1
In a high-pressure reaction kettle, catalyzing NEC hydrogenation by using Ru/Al 2O3 catalyst to obtain hydrogen-rich H 12 -NEC, and centrifugally separating.
H 12-NEC、NaAlH4、Ni(COD)2 in the hydrogen-rich state was reacted under an inert atmosphere according to 1:1: mixing at a molar ratio of 0.005 (2.07 g:0.54 g:0.014 g), adding gamma-Al 2O3 (0.131 g) with particle size of 20 nm, which is 5-wt% of the total mass of the substances, placing the mixture into a high-pressure reaction kettle, stirring and mixing the mixture uniformly by using a magnet, keeping a stirring state all the time, vacuumizing and detecting leakage, heating to 80 ℃, preserving heat for reaction at 2 h, introducing 0.1 MPa H 2, heating to 200 ℃ immediately, and measuring the generated gas condition by using a mass flowmeter with a one-way valve to obtain a hydrogen release curve. After no more hydrogen is produced, the temperature is reduced to 180 ℃,10 MPa H 2 is filled after the temperature is stable, and a pressure sensor is used for measuring the pressure change to obtain a hydrogen absorption curve. The results show that: the hydrogen desorption reaction can desorb 5.0 wt% of hydrogen from 10 h under the conditions of 200 ℃ and 0.1 MPa H 2 (the theoretical hydrogen storage amount is 5.4 wt%), and the corresponding hydrogen desorption reaction can desorb 4.9 wt% of hydrogen from 6 h under the conditions of 180 ℃ and 10 MPa H 2, which indicates that NaAlH 4 has partial hydrogen capable of being desorbed at the temperature and does not desorb, and indicates that the catalytic effect of nano Ni on NaAlH 4 is weak.
Comparative example 2
In a high-pressure reaction kettle, catalyzing NEC hydrogenation by using Ru/Al 2O3 catalyst to obtain hydrogen-rich H 12 -NEC, and centrifugally separating.
H 12-NEC、NaAlH4、Ti(OBu)4 in the hydrogen-rich state was reacted under an inert atmosphere according to 1:1: mixing at a molar ratio of 0.005 (2.07 g:0.54 g:0.017 g), adding gamma-Al 2O3 (0.131 g) with particle size of 20 nm, which is 5-wt% of the total mass of the substances, placing the mixture into a high-pressure reaction kettle, stirring and mixing the mixture uniformly by using a magnet, keeping a stirring state all the time, vacuumizing and detecting leakage, heating to 80 ℃, preserving heat for reaction at 2h, introducing 0.1 MPa H 2, heating to 200 ℃ immediately, and measuring the generated gas condition by using a mass flowmeter with a one-way valve to obtain a hydrogen release curve. After no more hydrogen is produced, the temperature is reduced to 180 ℃,10 MPa H 2 is filled after the temperature is stable, and a pressure sensor is used for measuring the pressure change to obtain a hydrogen absorption curve. The results show that: the hydrogen desorption reaction can release 1.0 wt% of 20 min hydrogen at 200 ℃ and 0.1 MPa H 2% (the theoretical hydrogen storage amount is 5.4 wt%), and the corresponding hydrogen desorption reaction can absorb 1.0 wt% of 1h hydrogen at 180 ℃ and 10 MPa H 2, which indicates that only NaAlH 4 is used for hydrogen desorption, and the nano Ti cannot catalyze NEC hydrogen desorption.
Comparative example 3
In a high-pressure reaction kettle, catalyzing 2-MID hydrogenation by using Ru/Al 2O3 catalyst to obtain H 8 -2-MID in a hydrogen-rich state, and separating by centrifugation.
H 8-2-MID、NaAlH4、Ni(COD)2、Ti(OBu)4 in the hydrogen-rich state was reacted under an inert atmosphere according to 1:0.334:0.005: mixing at a molar ratio of 0.005 (6.96 g:0.90 g:0.069 g:0.085 g), adding gamma-Al 2O3 (0.40 g) with particle size of 20 nm, which is 5-wt% of the total mass of the materials, placing the materials in a high-pressure reaction kettle, stirring and mixing uniformly by using a magnet, keeping a stirring state all the time, vacuumizing and detecting leakage, heating to 80 ℃, preserving heat for reaction at 2h, introducing 0.1 MPa H 2, heating to 200 ℃ immediately, and measuring the generated gas condition by using a mass flowmeter with a one-way valve to obtain a hydrogen release curve. After no more hydrogen is produced, the temperature is reduced to 180 ℃,5 MPa H 2 is filled after the temperature is stable, and a pressure sensor is used for measuring the pressure change to obtain a hydrogen absorption curve. Cooling to room temperature after no hydrogen absorption, vacuumizing, then introducing 0.1 MPa H 2, immediately heating to 200 ℃, measuring the generated gas condition by using a mass flowmeter with a one-way valve, and repeating the steps, thereby measuring the cyclic hydrogen absorption and desorption performance. The results showed that the hydrogen evolution was essentially complete at 1h and the evolution exceeded 5.9: 5.9 wt%, but the hydrogen evolution was very slow and the hydrogen evolution was only 2.3: 2.3 wt% at 10: 10 h, probably because the resulting 2-methylindole aluminum was still solid at the hydrogen evolution temperature and mass transfer was too slow. Whereas the 2-methylindole aluminum produced in example 2 was soluble in the excess 2-methylindole, this problem did not occur.
Comparative example 4
In a high-pressure reaction kettle, catalyzing NEC hydrogenation by using Ru/Al 2O3 catalyst to obtain hydrogen-rich H 12 -NEC, and centrifugally separating.
H 12-NEC、NaAlH4、Ni(COD)2、Ti(OBu)4 in the hydrogen-rich state was reacted under an inert atmosphere according to 1:4:0.01: mixing at a molar ratio of 0.01 (2.07 g:2.16 g:0.028 g:0.034 g), adding graphene (0.107, g) accounting for 2.5-wt% of the total mass of the substances, placing the mixture into a high-pressure reaction kettle, stirring and mixing the mixture uniformly by using a magnet, keeping a stirring state all the time, vacuumizing and detecting leakage, heating to 80 ℃, preserving heat for reaction 2 h, introducing 0.1 MPa H 2, heating to 200 ℃ immediately, and measuring the generated gas condition by using a mass flowmeter with a one-way valve to obtain a hydrogen release curve. After no more hydrogen is produced, the temperature is reduced to 180 ℃, 10 MPa H 2 is filled after the temperature is stable, and a pressure sensor is used for measuring the pressure change to obtain a hydrogen absorption curve. The results show that: the hydrogen release reaction can only release 1.4 wt% of hydrogen at 200 ℃ and 0.1 MPa H 2, the corresponding hydrogen absorption reaction can only absorb 1.1 wt% of hydrogen at 180 ℃ and 10 MPa H 2, and the analysis is based on the phenomenon observed during mixing, because the LOHC addition amount is too small, the whole system is more similar to a solid state, the in-situ generated catalyst has poor dispersing effect, and the mass transfer efficiency in the reaction process is low.
Claims (5)
1. A slurry hydrogen storage material, characterized in that: the slurry hydrogen storage material is prepared by mixing a hydrogen-rich liquid organic hydrogen carrier LOHC, a solid hydride NaAlH 4, a Ni-based catalyst precursor, a Ti-based catalyst precursor and a catalyst carrier;
The hydrogen-rich liquid organic hydrogen carrier LOHC is one selected from dodecahydro N-ethylcarbazole H 12 -NEC, octahydro 2-methylindole H 8 -2-MID or octahydro 1-methylindole H 8 -1-MID;
the Ni-based catalyst precursor is bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2, and the Ti-based catalyst precursor is tetrabutyl titanate Ti (OBu) 4;
the catalyst carrier is selected from one of Al 2O3、SiO2 or graphene;
The molar ratio of the hydrogen-rich liquid organic hydrogen carrier LOHC, the solid hydride NaAlH 4、Ni(COD)2 and Ti (OBu) 4 is 1: (0.1 to 1): (0.005-0.01): (0.005-0.01);
The dosage of the catalyst carrier is 2.5-5 wt% of the total mass of the hydrogen-rich liquid organic hydrogen carrier LOHC, the solid hydride NaAlH 4, the Ni-based catalyst precursor and the Ti-based catalyst precursor.
2. The slurry hydrogen storage material according to claim 1, wherein: the hydrogen-rich liquid organic hydrogen carrier LOHC is obtained by catalyzing LOHC hydrogenation by using a Ru/Al 2O3 catalyst in a high-pressure reaction kettle.
3. A method of preparing the slurry hydrogen storage material of claim 1, wherein: the preparation method comprises the following steps:
1) Preparation of hydrogen-rich liquid organic hydrogen carrier LOHC
In a high-pressure reaction kettle, catalyzing LOHC by using a Ru/Al 2O3 catalyst to hydrogenate to obtain LOHC in a hydrogen-rich state;
2) Preparation of slurry hydrogen storage material
And (3) mixing the hydrogen-rich LOHC, the solid hydride NaAlH 4, the Ni-based catalyst precursor and the Ti-based catalyst precursor prepared in the step (1) in an inert atmosphere in proportion, adding a catalyst carrier, and placing in a high-pressure reaction kettle to be uniformly mixed.
4. The method for producing a slurry hydrogen storage material according to claim 3, wherein: the hydrogen-rich liquid organic hydrogen carrier LOHC is one selected from dodecahydro N-ethylcarbazole H 12 -NEC, octahydro 2-methylindole H 8 -2-MID or octahydro 1-methylindole H 8 -1-MID; the Ni-based catalyst precursor is bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2, and the Ti-based catalyst precursor is tetrabutyl titanate Ti (OBu) 4; the catalyst carrier is selected from one of Al 2O3、SiO2 or graphene.
5. The method for producing a slurry hydrogen occluding material as recited in claim 4, wherein: the molar ratio of the LOHC in the hydrogen-rich state, the NaAlH 4 solid hydride, the Ni-based catalyst precursor bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2 and the Ti-based catalyst precursor tetrabutyl titanate Ti (OBu) 4 is 1: (0.1 to 1): (0.005-0.01): (0.005-0.01); the dosage of the catalyst carrier is 2.5-5wt% of the sum of the total mass of hydrogen-rich LOHC, solid hydride NaAlH 4, ni-based catalyst precursor bis- (1, 5-cyclooctadiene) Ni (COD) 2 and Ti-based catalyst precursor tetrabutyl titanate Ti (OBu) 4.
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