CN114804020A - Slurry hydrogen storage material and preparation method thereof - Google Patents
Slurry hydrogen storage material and preparation method thereof Download PDFInfo
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- CN114804020A CN114804020A CN202210565846.4A CN202210565846A CN114804020A CN 114804020 A CN114804020 A CN 114804020A CN 202210565846 A CN202210565846 A CN 202210565846A CN 114804020 A CN114804020 A CN 114804020A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 252
- 239000001257 hydrogen Substances 0.000 title claims abstract description 252
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 238
- 239000011232 storage material Substances 0.000 title claims abstract description 51
- 239000002002 slurry Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 32
- 150000004678 hydrides Chemical class 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 42
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 12
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical compound C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 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 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
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910021389 graphene Inorganic materials 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 54
- 238000003795 desorption Methods 0.000 abstract description 31
- 238000003860 storage Methods 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 10
- 239000007791 liquid phase Substances 0.000 abstract description 8
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 16
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002245 particle Substances 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
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 2-methylindolyl aluminum Chemical compound 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 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
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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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
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a slurry hydrogen storage material and a preparation method thereof. The slurry hydrogen storage material is prepared from a hydrogen-rich liquid organic hydrogen carrier LOHC and a solid hydride NaAlH 4 The catalyst is prepared by mixing a Ni-based catalyst precursor, a Ti-based catalyst precursor and a catalyst carrier. The invention firstly uses liquid phase organic hydrogen carrier (LOHC) and solid hydride hydrogen storage material NaAlH 4 The novel slurry hydrogen storage material is prepared by compounding, the hydrogen storage capacity of the two materials is higher, and the hydrogen absorption and desorption temperature is close to each other, so that the high hydrogen storage capacity (more than 5.0 wt%), the lower operation temperature (lower than 200 ℃) and the faster hydrogen absorption and desorption dynamics are ensured simultaneously, and the liquid-phase organic hydrogen carrier LOHC and the solid hydride NaAlH are realized 4 The material has good application prospect and can avoid the disadvantages.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a slurry hydrogen storage material and a preparation method thereof.
Background
The hydrogen energy is expected in recent decades due to a series of advantages such as cleanness, no pollution, high heat value and the like, and is considered as an indispensable part for solving the energy problem and developing low-carbon economy by many people. Although hydrogen energy is being developed vigorously, the key issues of hydrogen production, storage and fuel cells are not well addressed. Particularly, the method is used for storing hydrogen which plays a role of a bridge between hydrogen preparation and application, and a particularly mature hydrogen storage mode which can be widely applied is not provided. The existing vehicle-mounted hydrogen storage mode is 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 capacity, safety and the like. Therefore, the lack of efficient hydrogen storage materials can be said to be a bottleneck problem to be solved in the development of hydrogen energy.
At present, Liquid Organic Hydrogen Carrier (LOHC) and solid hydride are two types of hydrogen storage materials which are considered to be possible to solve the hydrogen storage problem, but the main disadvantage of the liquid organic hydrogen carrier is poor hydrogen absorption and desorption kinetics, while the main disadvantage of the solid hydride is that the material with high hydrogen storage capacity generally has high hydrogen absorption and desorption temperature, and the management of heat conduction and volume change is difficult. In view of the above, researchers have proposed that these two types of hydrogen storage materials are compounded to form a slurry-like hydrogen storage material, which may improve the advantages and reduce the disadvantages and obtain a hydrogen storage material with more excellent performance. For example, a patent application (CN 1380136 a) at the university of zhejiang, 2002 proposes a slurry-like hydrogen storage material, in which a liquid-phase organic hydrogen carrier such as benzene, toluene, naphthalene, etc. can be added to a solid hydride hydrogen storage material to form a solid-liquid mixed slurry, which can effectively solve the problems of heat transfer and volume change of the solid hydride, however, since the liquid-phase organic hydrogen carrier selected by them has a very high hydrogen desorption temperature and poor kinetics, they are said to be a high-efficiency hydrogen storage material with 6.5 wt% hydrogen storage capacity only considering the hydrogen absorption process, and actually should only absorb hydrogen very slowly, but have a slower hydrogen desorption rate, and have a low practical value.
The subject group has filed a patent application (CN 111013593 a) showing: n-doped aromatic compound liquid organic hydrogen carriers such as N-ethyl carbazole, 2-methylindole, 1-methylindole and the like can realize rapid 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 hydrogen absorption and desorption kinetics of liquid organic hydrogen carrier, difficult heat transfer of solid hydride hydrogen storage material and volume change in hydrogen absorption and desorption process under the condition of ensuring high hydrogen storage capacity (more than 5.0 wt%), lower operating temperature (less than 200 ℃) and faster hydrogen absorption and desorption kinetics is a new research direction provided by the subject group and is also a technical bottleneck which is urgently needed to be overcome in the prior art of the hydrogen storage material.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a slurry-like hydrogen storage material which is based on liquid organic hydrogen carriers LOHC such as N-ethylcarbazole, methylindole and the like and solid hydride NaAlH 4 A novel composite slurry hydrogen storage material.
Another object of the present invention is to provide a method for producing a slurry-like hydrogen storage material.
The technical scheme adopted for realizing one purpose of the invention is as follows: the slurry hydrogen storage material is prepared from liquid organic hydrogen carrier LOHC in hydrogen-rich state and solid hydride NaAlH 4 The catalyst is prepared by mixing a Ni-based catalyst precursor, a Ti-based catalyst precursor and a catalyst carrier.
Preferably, the liquid organic hydrogen carrier LOHC in the hydrogen-rich state according to the invention is selected from the group consisting of dodecahydro-N-ethylcarbazole H 12 -NEC, octahydro 2-methylindole H 8 -2-MID or octahydro 1-methylindole H 8 -one of 1-MIDs.
Preferably, the Ni-based catalyst precursor of the present invention is bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2 The Ti-based catalyst precursor is tetrabutyl titanate Ti (OBu) 4 。
Preferably, the catalyst carrier of the present invention is selected from Al 2 O 3 、SiO 2 Or graphene.
Preferably, the hydrogen-rich liquid organic hydrogen carrier LOHC and the solid hydride NaAlH are provided by the invention 4 、Ni(COD) 2 And Ti (OBu) 4 In a molar ratio of 1: (0.1-1): (0.005-0.01): (0.005-0.01).
Preferably, the invention isThe catalyst carrier is liquid organic hydrogen carrier LOHC and solid hydride NaAlH 4 2.5 to 5 wt% of the sum of the total mass of the Ni-based catalyst precursor and the Ti-based catalyst precursor.
Preferably, the hydrogen-rich liquid organic hydrogen carrier LOHC is prepared by placing Ru/Al in a high-pressure reaction kettle 2 O 3 The catalyst is used for catalyzing LOHC hydrogenation to obtain the catalyst.
The technical scheme adopted for realizing the other purpose of the invention is as follows: a preparation method of a slurry hydrogen storage material comprises the following preparation steps:
1) preparation of liquid organic hydrogen carrier LOHC in hydrogen-rich state
In a high-pressure reaction kettle, Ru/Al is selected 2 O 3 Catalyzing LOHC hydrogenation by using a catalyst to obtain hydrogen-rich LOHC;
2) preparation of slurry-like hydrogen storage material
In an inert atmosphere, the LOHC in a hydrogen-rich state and the solid hydride NaAlH prepared in the step 1) are put in 4 Mixing the Ni-based catalyst precursor and the Ti-based catalyst precursor in proportion, adding the catalyst carrier, and placing the mixture in a high-pressure reaction kettle to be uniformly mixed.
Wherein the liquid organic hydrogen carrier in a hydrogen-rich state LOHC is selected from dodecahydro-N-ethylcarbazole H 12 -NEC, octahydro 2-methylindole H 8 -2-MID or octahydro 1-methylindole H 8 -one of 1-MID; the Ni-based catalyst precursor is bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2 The Ti-based catalyst precursor is tetrabutyl titanate Ti (OBu) 4 (ii) a The catalyst carrier is selected from Al 2 O 3 、SiO 2 Or graphene.
Wherein the hydrogen-rich LOHC and solid hydride NaAlH 4 Ni-based catalyst precursor bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2 Ti-based catalyst precursor tetrabutyl titanate Ti (OBu) 4 In a molar ratio of 1: (0.1-1): (0.005-0.01): (0.005-0.01); the dosage of the catalyst carrier is LOHC in a hydrogen-rich state and NaAlH in a solid hydride state 4 Ni-based catalyst precursor bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2 With a Ti-based catalyst precursor tetrabutyl titanate Ti (OBu) 4 2.5-5 wt% of the total mass.
Compared with the prior art, the invention has the following technical advantages:
(1) the invention firstly uses liquid phase organic hydrogen carrier (LOHC) and solid hydride hydrogen storage material NaAlH 4 The novel slurry hydrogen storage material is prepared by compounding, the hydrogen storage capacity of the two materials is higher, and the hydrogen absorption and desorption temperature is close to each other, so that the high hydrogen storage capacity (more than 5.0 wt%), the lower operation temperature (lower than 200 ℃) and the faster hydrogen absorption and desorption dynamics are ensured simultaneously, and the liquid-phase organic hydrogen carrier LOHC and the solid hydride NaAlH are realized 4 The material has good application prospect and can avoid the disadvantages.
(2) The invention is based on N-ethyl carbazole (NEC), 2-methylindole (2-MID), 1-methylindole (1-MID) and solid hydride hydrogen storage material NaAlH with high hydrogen storage capacity and low operation temperature 4 Preparing a novel slurry hydrogen storage material, and introducing a Ti-based catalyst precursor tetrabutyl titanate Ti (OBu) into the material in order to ensure rapid hydrogen absorption and desorption kinetics 4 And Ni-based catalyst precursor bis- (1, 5-cyclooctadiene) nickel as solid hydride hydrogen storage material NaAlH in an in-situ forming manner 4 And liquid phase organic hydrogen carrier LOHC, and NaAlH 4 Can be used as a cocatalyst of liquid-phase organic hydrogen carrier LOHC, and can reduce the hydrogen absorption and desorption temperature of the LOHC through reaction coupling 4 The reaction coupling of (2) realizes reversible hydrogen absorption and desorption at lower operation temperature (130 ℃) and high hydrogen storage (more than 5.0 wt%).
Drawings
FIG. 1 is a graph showing the change of the hydrogen absorption/desorption kinetic curve measured in example 1 of the present invention.
FIG. 2 is a diagram of an apparatus for testing hydrogen absorption/desorption kinetics curves according to the present invention.
FIG. 3 is a graph showing the change in the hydrogen absorption and desorption capacity in the cycle in example 2 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
The invention relates to a slurry hydrogen storage material, which is prepared from a hydrogen-rich liquid organic hydrogen carrier LOHC and a solid hydride NaAlH 4 The Ni-based catalyst precursor, the Ti-based catalyst precursor and the catalyst carrier are prepared by mixing, and the preparation method comprises the following specific steps:
1) preparation of liquid organic hydrogen carrier LOHC in hydrogen-rich state
In a high-pressure reaction kettle, Ru/Al is used 2 O 3 Catalyst catalyzed hydrogenation of LOHC to obtain hydrogen-rich LOHC (preferably for preparing dodecahydro-N-ethylcarbazole H) 12 -NEC, octahydro 2-methylindole H 8 -2-MID octahydro 1-methylindole H 8 -one of 1-MID) and separated by centrifugation.
2) Preparation of slurry-like hydrogen storage material
In an inert atmosphere, the LOHC in a hydrogen-rich state and the solid hydride NaAlH prepared in the step 1) are put in 4 Mixing Ni-based catalyst precursor and Ti-based catalyst precursor in proportion, and adding catalyst carrier (preferably Al) 2 O 3 、SiO 2 Or one of graphene) in a high-pressure reaction kettle.
Wherein, the hydrogen-rich LOHC and solid hydride hydrogen storage material NaAlH 4 The molar ratio of the Ni-based catalyst precursor to the Ti-based catalyst precursor is 1: (0.1-1): (0.005-0.01): (0.005-0.01); the dosage of the catalyst carrier is LOHC in a hydrogen-rich state and NaAlH in a solid hydride state 4 Ni-based catalyst precursor bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2 With a Ti-based catalyst precursor tetrabutyl titanate Ti (OBu) 4 2.5-5 wt% of the total mass.
The invention discloses a hydrogen absorption and desorption testing method of a slurry hydrogen storage material, which comprises the following steps:
in the preparation process of the slurry hydrogen storage material, uniformly stirring and mixing the slurry hydrogen storage material in a high-pressure reaction kettle by using magnetons, continuously keeping the stirring state, vacuumizing, detecting leakage, heating to 80 ℃, preserving heat for 2 hours, and then introducing H with the pressure of 0.1 MPa 2 And then heating to 130-200 ℃, and measuring the condition of the generated gas by using a mass flowmeter with a one-way valve to obtain a hydrogen discharge curve. After no hydrogen production is carried out, cooling to 120 toCharging 5-10 MPa H after the temperature is stable at 180 DEG C 2 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, and introducing 0.1 MPa H 2 And then, heating to 130-200 ℃, measuring the condition of the generated gas by using a mass flow meter with a one-way valve, and repeating the steps so as to measure the circular hydrogen absorption and desorption performance. The apparatus for testing the hydrogen absorption and desorption kinetics curves is shown in FIG. 2.
Wherein, under the reaction conditions of the reaction temperature of 80 ℃ and the heat preservation for 2 hours, Ni (COD) 2 And Ti (OBu) 4 Reducing into Ni/Ti composite catalyst (nano-Ni/Ti @ carrier catalyst), wherein NaAlH 4 Also acts as a reducing agent, while being hydrogen-rich in LOHC and Al 2 O 3 The catalyst carrier plays a role in preventing Ni and Ti from being agglomerated into larger particles. It is to be noted that the invention introduces the nano-Ni/Ti @ supported catalyst which is a hydrogen absorption and desorption catalyst into the slurry hydrogen storage material by in-situ formation for the first time, and the catalyst is a non-noble metal catalyst.
The invention contains LOHC in a hydrogen-rich state and a solid hydride hydrogen storage material NaAlH 4 The hydrogen absorption and desorption reaction process of the slurry hydrogen storage material is as follows:
the hydrogen discharge reaction process is as follows: h n -LOHC + NaAlH 4 → LOHC + NaH + Al + H 2 ；
The hydrogen absorption reaction process is as follows: LOHC + NaH + Al + H 2 → H n -LOHC + NaAlH 4 ；
Example 1
In a high-pressure reaction kettle, Ru/Al is used 2 O 3 The catalyst catalyzes N-ethyl carbazole (NEC) to be hydrogenated to obtain H in a hydrogen-rich state 12 NEC and separation by centrifugation.
In an inert atmosphere, H in a hydrogen-rich state 12 -NEC、NaAlH 4 、Ni(COD) 2 、Ti(OBu) 4 According to the following steps of 1: 1: 0.01: 0.01 (2.07 g: 0.54 g: 0.028 g: 0.034 g), adding 2.5 wt% of graphene (0.067 g) based on the total mass of the above components, placing the mixture in a high-pressure reaction kettle, stirring and mixing uniformly by using magnetons, and then keeping the stirring state all the time, whereinVacuumizing, detecting leakage, heating to 80 deg.C, reacting for 2 hr, and introducing 0.1 MPa H 2 Then, the temperature is raised to 200 ℃, and the condition of the generated gas is measured by a mass flowmeter with a one-way valve to obtain a hydrogen discharge curve. After no hydrogen production, the temperature is reduced to 180 ℃, and 10 MPa H is filled after the temperature is stable 2 And measuring the pressure change by using a pressure sensor to obtain a hydrogen absorption curve. The results are shown in FIG. 1, and the hydrogen evolution reaction can be carried out at a temperature of 200 ℃ and a pressure of 0.1 MPa H 2 Under the condition of (1), the hydrogen release time of 10H is close to 5.5 wt% (the hydrogen yield is close to 100%), and the corresponding hydrogen absorption reaction can be carried out at 180 ℃ and 10 MPa H 2 The hydrogen absorption time of 10 hours under the condition (1) is more than 5.4 wt percent. The hydrogen absorption and desorption process has several stages with different rates, probably because of H 12 -NEC and NaAlH 4 There are multiple hydrogen absorption and desorption processes, resulting from different kinetics of the different processes. The hydrogen absorption and desorption processes are as follows:
6NaAlH 4 = 2Na 3 AlH 6 + 4Al + 6H 2 ；
2Na 3 AlH 6 = 6NaH + 2Al + 3H 2 ；
C 14 H 25 N = C 14 H 21 N + 2H 2 ；
C 14 H 21 N = C 14 H 17 N + 2H 2 ；
C 14 H 17 N = C 14 H 13 N + 2H 2 。
example 2
In a high-pressure reaction kettle, Ru/Al is used 2 O 3 The catalyst catalyzes 2-methylindole (2-MID) to be hydrogenated to obtain H in a hydrogen-rich state 8 -2-MID and separated by centrifugation.
In an inert atmosphere, H in a hydrogen-rich state 8 -2-MID、NaAlH 4 、Ni(COD) 2 、Ti(OBu) 4 According to the following steps of 1: 0.1: 0.005: 0.005 (6.96 g: 0.27 g: 0.069 g: 0.085 g) was mixed, and γ -Al having a particle size of 20 nm was added in an amount of 5 wt% of the total mass 2 O 3 (0.40 g), placing the mixture in a high-pressure reaction kettle, stirring and mixing the mixture uniformly by using magnetons, keeping the stirring state all the time, and vacuumizing the kettleAfter leakage detection, heating to 80 ℃, reacting for 2 hours in a heat preservation way, and then introducing 0.1 MPa H 2 Then, the temperature is raised to 200 ℃, and the condition of the generated gas is measured by a mass flowmeter with a one-way valve to obtain a hydrogen discharge curve. After no hydrogen production, the temperature is reduced to 180 ℃, and 5 MPa H is filled after the temperature is stable 2 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, and introducing 0.1 MPa H 2 Then the temperature is raised to 200 ℃, the condition of the generated gas is measured by a mass flowmeter with a one-way valve, and the process is repeated, thereby measuring the hydrogen absorbing and releasing performance of the cycle. The results show that: the hydrogen discharging can be basically finished within 4 h, the hydrogen absorbing can be finished within 2 h, the hydrogen storage capacity is only slightly attenuated after 5 times of hydrogen absorbing and discharging, and the capacity change of the circular hydrogen absorbing and discharging is shown in figure 3. The amount of hydrogen first absorbed and desorbed exceeds 5.9 wt%, and exceeds the expected theoretical hydrogen storage amount of 5.8 wt%, which may be due to NaAlH 4 And H in a hydrogen-rich state 8 The active hydrogen on the-2-MID (H on the N-H bond) is reacted, i.e.the possible course of the reaction is:
10 
+NaAlH 4 = 
+ 7 
+ NaH + 43H 2
this indicates LOHC and NaAlH 4 The hydrogen absorption and desorption reactions have certain reaction coupling and can be mutually promoted. The same feed as in the example was used, and the hydrogen discharge conditions were changed to 130 ℃ and 0.1 MPa H 2 The hydrogen absorption condition is changed to 130 ℃ and 10 MPa H 2 The hydrogen desorption amount measured in 10 hours is 5.1 wt%, and the hydrogen absorption amount measured in 6 hours is 5.0 wt%, and a slurry-like hydrogen storage system having reversible hydrogen absorption and desorption of more than 5.0 wt% at 130 ℃ is realized for the first time.
Example 3
In a high-pressure reaction kettle, Ru/Al is used 2 O 3 The catalyst catalyzes 1-MID to hydrogenate to obtain H in a hydrogen-rich state 8 -1MID and separation by centrifugation.
In an inert atmosphere, H in a hydrogen-rich state 8 -1-MID、NaAlH 4 、Ni(COD) 2 、Ti(OBu) 4 According to the following steps of 1: 0.1: 0.005: 0.005 (6.96 g: 0.27 g: 0.069 g: 0.085 g) was mixed, and nano SiO in an amount of 4 wt% of the total mass of these materials was added 2 (0.295 g), placing the mixture in a high-pressure reaction kettle, stirring and mixing the mixture uniformly by using magnetons, keeping the stirring state all the time, vacuumizing, detecting leakage, heating to 80 ℃, keeping the temperature for reaction for 2 hours, and then introducing 0.1 MPa H 2 Then the temperature is raised to 180 ℃, and the condition of the generated gas is measured by a mass flowmeter with a one-way valve to obtain a hydrogen discharge curve. After no hydrogen production, the temperature is reduced to 150 ℃, and 7 MPa H is filled after the temperature is stable 2 And measuring the pressure change by using a pressure sensor to obtain a hydrogen absorption curve. The results show that: the hydrogen release energy is basically completed within 8 h (5.3 wt% of hydrogen release), the hydrogen absorption energy is completed within 3 h (5.1 wt% of hydrogen absorption), and the total reaction process is as follows:
20 
+ 2NaAlH 4 = 20 
+ 2NaH + 2Al + 83H 2 。
comparative example 1
In a high-pressure reaction kettle, Ru/Al is used 2 O 3 Hydrogenation of NEC catalyzed by catalyst to obtain H in hydrogen-rich state 12 NEC and separation by centrifugation.
In an inert atmosphere, H in a hydrogen-rich state 12 -NEC、NaAlH 4 、Ni(COD) 2 According to the following steps of 1: 1: 0.005 (2.07 g: 0.54 g: 0.014 g) was mixed, and 5 wt% of γ -Al having a particle size of 20 nm was added to the mixture 2 O 3 (0.131 g), placing the mixture in a high-pressure reaction kettle, stirring and mixing the mixture uniformly by using magnetons, keeping the stirring state all the time, vacuumizing, detecting leakage, heating to 80 ℃, keeping the temperature for reaction for 2 hours, and introducing 0.1 MPa H 2 Immediately raising the temperature to 200 ℃ by using a check valveThe mass flowmeter measures the generated gas condition to obtain a hydrogen discharge curve. After no hydrogen production, the temperature is reduced to 180 ℃, and 10 MPa H is filled after the temperature is stable 2 And measuring the pressure change by using a pressure sensor to obtain a hydrogen absorption curve. The results show that: the hydrogen discharge reaction can be carried out at 200 ℃ and 0.1 MPa H 2 Under the condition of (1), hydrogen is released for 10H by 5.0 wt percent (the theoretical hydrogen storage amount is 5.4 wt percent), and the corresponding hydrogen absorption reaction can be carried out at 180 ℃ under 10 MPa H 2 The hydrogen absorption was 4.9 wt% for 6 hours, which indicates that NaAlH 4 Some hydrogen capable of being absorbed and released at the temperature is not absorbed and released, which shows that nano Ni is absorbed and released to NaAlH 4 The catalytic effect of hydrogen absorption and desorption is very weak.
Comparative example 2
In a high-pressure reaction kettle, Ru/Al is used 2 O 3 Hydrogenation of NEC catalyzed by catalyst to obtain H in hydrogen-rich state 12 NEC and separation by centrifugation.
In an inert atmosphere, H in a hydrogen-rich state 12 -NEC、NaAlH 4 、Ti(OBu) 4 According to the following steps of 1: 1: 0.005 (2.07 g: 0.54 g: 0.017 g) was mixed, and 20 nm-diameter gamma-Al was added in an amount of 5 wt% based on the total mass of these materials 2 O 3 (0.131 g), placing the mixture in a high-pressure reaction kettle, stirring and mixing the mixture uniformly by using magnetons, keeping the stirring state all the time, vacuumizing, detecting leakage, heating to 80 ℃, keeping the temperature for reaction for 2 hours, and introducing 0.1 MPa H 2 Then, the temperature is raised to 200 ℃, and the condition of the generated gas is measured by a mass flowmeter with a one-way valve to obtain a hydrogen discharge curve. After no hydrogen production, the temperature is reduced to 180 ℃, and 10 MPa H is filled after the temperature is stable 2 And measuring the pressure change by using a pressure sensor to obtain a hydrogen absorption curve. The results show that: the hydrogen discharge reaction can be carried out at 200 ℃ and 0.1 MPa H 2 Under the condition of (1.0) wt% hydrogen release in 20 min (theoretical hydrogen storage amount is 5.4 wt%), the corresponding hydrogen absorption reaction can be carried out at 180 ℃ under 10 MPa H 2 1 h hydrogen uptake under the conditions of (1.0 wt%), which indicates that only NaAlH is present 4 And hydrogen absorption and desorption occur, which shows that the nano Ti can not catalyze the NEC to absorb and desorb hydrogen.
Comparative example 3
In a high-pressure reaction kettle, Ru/Al is used 2 O 3 Catalyzing 2-MID hydrogenation by catalyst to obtain hydrogen-rich stateH of (A) to (B) 8 2-MID and separated by centrifugation.
In an inert atmosphere, H in a hydrogen-rich state 8 -2-MID、NaAlH 4 、Ni(COD) 2 、Ti(OBu) 4 According to the following steps of 1: 0.334: 0.005: 0.005 (6.96 g: 0.90 g: 0.069 g: 0.085 g) was mixed, and 5 wt% of the total mass of these materials was added, together with gamma-Al having a particle size of 20 nm 2 O 3 (0.40 g), placing the mixture into a high-pressure reaction kettle, stirring and mixing the mixture uniformly by using magnetons, keeping the stirring state all the time, vacuumizing, detecting leakage, heating to 80 ℃, keeping the temperature for reacting for 2 hours, and introducing H with 0.1 MPa 2 Then, the temperature is raised to 200 ℃, and the condition of the generated gas is measured by a mass flowmeter with a one-way valve to obtain a hydrogen discharge curve. After no hydrogen production, the temperature is reduced to 180 ℃, and 5 MPa H is filled after the temperature is stable 2 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, and introducing 0.1 MPa H 2 Then the temperature is raised to 200 ℃, the condition of the generated gas is measured by a mass flowmeter with a one-way valve, and the process is repeated, thereby measuring the hydrogen absorbing and releasing performance of the cycle. The results showed that the hydrogen release was substantially completed in 1 hour, the hydrogen release amount exceeded 5.9 wt%, but the hydrogen absorption was slow, and the hydrogen absorption amount was only 2.3 wt% in 10 hours, which is probably caused by the fact that the produced 2-methylindolyl aluminum was still solid at the hydrogen absorption temperature and the mass transfer was too slow. The 2-methylindolyl aluminum formed in example 2 was soluble in the excess 2-methylindole and did not show this problem.
Comparative example 4
In a high-pressure reaction kettle, Ru/Al is used 2 O 3 Hydrogenation of NEC catalyzed by catalyst to obtain H in hydrogen-rich state 12 NEC and separation by centrifugation.
In an inert atmosphere, H in a hydrogen-rich state 12 -NEC、NaAlH 4 、Ni(COD) 2 、Ti(OBu) 4 According to the following steps of 1: 4: 0.01: 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 materials, placing the mixture in a high-pressure reaction kettle, uniformly stirring and mixing the mixture by using magnetons, keeping the stirring state all the time, vacuumizing, detecting the leakage, and then obtaining the productHeating to 80 ℃, reacting for 2H under heat preservation, and then introducing 0.1 MPa H 2 Then, the temperature is raised to 200 ℃, and the condition of the generated gas is measured by a mass flowmeter with a one-way valve to obtain a hydrogen discharge curve. After no hydrogen production, the temperature is reduced to 180 ℃, and 10 MPa H is filled after the temperature is stable 2 And measuring the pressure change by using a pressure sensor to obtain a hydrogen absorption curve. The results show that: the hydrogen discharge reaction can be carried out at 200 ℃ and 0.1 MPa H 2 Under the condition of (1.4 wt%) of hydrogen can be discharged after 10 hr, and the correspondent hydrogen-absorbing reaction can be implemented at 180 deg.C and 10 MPa H 2 The hydrogen absorption at 10 hours of (1.1 wt%) was observed, and this was analyzed from the phenomenon observed during mixing because the amount of LOHC added was too small, the whole system was closer to a solid state, the dispersion effect of the in-situ formed catalyst was poor, and the mass transfer efficiency during the reaction was low.
Claims (10)
1. A slurry hydrogen storage material, characterized by: the slurry hydrogen storage material is prepared from a hydrogen-rich liquid organic hydrogen carrier LOHC and a solid hydride NaAlH 4 The catalyst is prepared by mixing a Ni-based catalyst precursor, a Ti-based catalyst precursor and a catalyst carrier.
2. The slurried hydrogen storage material as recited in claim 1, wherein: the liquid organic hydrogen carrier in a hydrogen-rich state LOHC is selected from dodecahydro-N-ethylcarbazole H 12 -NEC, octahydro 2-methylindole H 8 -2-MID or octahydro 1-methylindole H 8 -one of 1-MIDs.
3. The slurried hydrogen storage material as recited in claim 1, wherein: the Ni-based catalyst precursor is bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2 The Ti-based catalyst precursor is tetrabutyl titanate Ti (OBu) 4 。
4. The slurried hydrogen storage material as recited in claim 1, wherein: the catalyst carrier is selected from Al 2 O 3 、SiO 2 Or graphene.
5. The slurried hydrogen storage material as recited in claim 3, wherein: the liquid state organic hydrogen carrier LOHC and the solid hydride NaAlH in the hydrogen-rich state 4 、Ni(COD) 2 And Ti (OBu) 4 In a molar ratio of 1: (0.1-1): (0.005-0.01): (0.005-0.01).
6. The slurried hydrogen storage material as recited in claim 4, wherein: the dosage of the catalyst carrier is liquid organic hydrogen carrier LOHC and solid hydride NaAlH in a hydrogen-rich state 4 2.5 to 5 wt% of the sum of the total mass of the Ni-based catalyst precursor and the Ti-based catalyst precursor.
7. The slurry hydrogen storage material according to any one of claims 1 to 6, characterized in that: the liquid state organic hydrogen carrier LOHC with rich hydrogen is prepared by placing Ru/Al in a high-pressure reaction kettle 2 O 3 The catalyst is used for catalyzing LOHC hydrogenation to obtain the catalyst.
8. A method of producing the slurry hydrogen storage material of claim 1, characterized by: the preparation steps are as follows:
preparation of liquid organic hydrogen carrier LOHC in hydrogen-rich state
In a high-pressure reaction kettle, Ru/Al is selected 2 O 3 Catalyzing LOHC hydrogenation by using a catalyst to obtain hydrogen-rich LOHC;
preparation of slurry-like hydrogen storage material
In an inert atmosphere, the LOHC in a hydrogen-rich state and the solid hydride NaAlH prepared in the step 1) are put in 4 Mixing the Ni-based catalyst precursor and the Ti-based catalyst precursor in proportion, adding the catalyst carrier, and placing the mixture in a high-pressure reaction kettle to be uniformly mixed.
9. The method for producing a slurry hydrogen storage material according to claim 8, characterized in that: the liquid organic hydrogen carrier in a hydrogen-rich state LOHC is selected from dodecahydro-N-ethylcarbazole H 12 -NEC, octahydro 2-methylindole H 8 -2-MID or octahydro 1-methylindole H 8 -one of 1-MID; the Ni-based catalyst precursorIs bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2 The Ti-based catalyst precursor is tetrabutyl titanate Ti (OBu) 4 (ii) a The catalyst carrier is selected from Al 2 O 3 、SiO 2 Or graphene.
10. The method for producing a slurry hydrogen storage material according to claim 9, characterized in that: the LOHC in a hydrogen-rich state and the solid hydride NaAlH 4 Ni-based catalyst precursor bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2 Ti-based catalyst precursor tetrabutyl titanate Ti (OBu) 4 In a molar ratio of 1: (0.1-1): (0.005-0.01): (0.005-0.01); the dosage of the catalyst carrier is LOHC in a hydrogen-rich state and NaAlH in a solid hydride state 4 Ni-based catalyst precursor bis- (1, 5-cyclooctadiene) nickel Ni (COD) 2 With a Ti-based catalyst precursor tetrabutyl titanate Ti (OBu) 4 2.5-5 wt% of the total mass.
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