CN115069289A - Preparation method of hydrazine hydrate dehydrogenation catalyst - Google Patents
Preparation method of hydrazine hydrate dehydrogenation catalyst Download PDFInfo
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- CN115069289A CN115069289A CN202210803949.XA CN202210803949A CN115069289A CN 115069289 A CN115069289 A CN 115069289A CN 202210803949 A CN202210803949 A CN 202210803949A CN 115069289 A CN115069289 A CN 115069289A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 title claims abstract description 39
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 87
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 87
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000002923 metal particle Substances 0.000 claims abstract description 7
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 4
- 229910002056 binary alloy Inorganic materials 0.000 claims abstract description 4
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000011282 treatment Methods 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 238000011221 initial treatment Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 150000003057 platinum Chemical class 0.000 claims description 5
- 150000003283 rhodium Chemical class 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000000969 carrier Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052697 platinum Inorganic materials 0.000 abstract description 7
- 239000010948 rhodium Substances 0.000 abstract description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 238000007306 functionalization reaction Methods 0.000 abstract description 5
- 229910000629 Rh alloy Inorganic materials 0.000 abstract description 4
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 125000003368 amide group Chemical group 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 25
- 239000000956 alloy Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910002844 PtNi Inorganic materials 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000013177 MIL-101 Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001408 amides Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/23—
-
- B01J35/393—
-
- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
Abstract
The invention discloses a preparation method of a hydrazine hydrate dehydrogenation catalyst. The invention uses urea to carry out heat treatment on the carbon nano tube twice continuously at a lower temperature to prepare the amino functionalized carbon nano tube as a carrier, and further uses sodium borohydride as a reducing agent to reduce metal salt into metal particles which are loaded on the amino functionalized carbon nano tube carrier, wherein the metal particle size is less than 3 nanometers. The preparation process is simple, no strong acid, strong alkali and other polluting liquids exist, the carbon nano tube carrier after amino functionalization has amino and amido functional groups and pyridine nitrogen doped into the carbon nano tube, the catalytic performance of platinum or rhodium and binary alloy of platinum or rhodium and other metals is greatly improved, the hydrogen production performance of the decomposition of hydrazine hydrate exceeds that of other commercial catalysts, and the catalyst material with high efficiency is provided for preparing hydrogen by industrial hydrazine hydrate.
Description
Technical Field
The invention relates to the field of catalyst synthesis, in particular to a preparation method of a catalyst for preparing hydrogen by catalyzing hydrazine hydrate dehydrogenation.
Background
Under the influence of factors such as global warming and constant consumption of non-renewable fossil energy, the global energy consumption structure is changing to low-carbon. Hydrogen energy is a secondary energy with high energy density and no pollution, and is widely regarded by various countries in the world. The hydrogen energy is expected to be comprehensively integrated into the energy demand side in the fields of traffic, industry and the like in the future.
The current sources of hydrogen production are: preparing hydrogen from coal; natural substance (such as natural gas)Hydrogen is produced by gas; preparing hydrogen from methanol; industrial by-product hydrogen production; hydrogen production by renewable energy sources, and the like. Among them, hydrazine hydrate is considered as a hydrogen storage and production material with great application potential. Hydrazine hydrate (N) 2 H 4 ·H 2 O) has a high hydrogen storage density (8.0 wt%), and is completely dehydrogenated to generate hydrogen (H) 2 ) And nitrogen (N) 2 ) The material has the advantages of stable liquid state in the temperature range of 213-392K, and the like, and is considered to be a hydrogen storage material with great application potential. The catalyst can be used for quickly and completely dehydrogenating hydrazine hydrate to generate hydrogen and nitrogen in a stable solution system in a lower temperature range (273- & ltSUB & gt 353K). The catalysts are classified into homogeneous and heterogeneous catalysts. The homogeneous catalyst has high reaction activity and good selectivity, but the design of a reaction device is more complex due to homogeneous phase. The heterogeneous catalyst mainly comprises noble metals of platinum and rhodium, has good stability and easier preparation, can greatly simplify hydrogen production equipment, and is beneficial to practical application.
Researchers have developed a plurality of heterogeneous reaction catalysts with good performance for hydrazine hydrate dehydrogenation, and 2012, Wang et al have experimentally concluded that nano alloy particles composed of RhNi are used as catalytic metals, and graphene is used as a carrier of nano particles, and the catalyst composed of the RhNi and the graphene is used for catalyzing and decomposing hydrazine hydrate to produce hydrogen with hydrogen selectivity as high as 100%, and has extremely high catalytic activity. The Lu topic composition successfully synthesized RhNi nanoparticles (RhNi/MIL-101) with an average size of 2.8nm uniformly dispersed on MIL-101, while the carrier MIL-101 had a high surface area to promote reactant adsorption and a porous structure to facilitate mass transfer. At 50 ℃, the RhNi/MIL-101 catalyst catalyzes hydrazine hydrate to be completely decomposed, and the conversion rate value reaches 428.6h -1 . Preparation of TiO by Lu subject group 2 Modified Ti 3 C 2 T x The nano-sheet is used for loading NiPt nano-particles, and the conversion rate value is up to 1220h -1 . The supported composite catalyst can limit the size of metal particles, improve the dispersibility of the metal particles, provide more catalytic active sites, and generate the interaction of electrons between some carriers and metal nano particles, so that the catalyst shows better catalytic activity and hydrogen selectivity.
Carbon nanotubes are a carbon structure material whose appearance can be viewed as being formed by the crimping of a graphite sheet into a tube shape. And can be divided into multi-wall carbon nanotubes and single-wall carbon nanotubes according to the number of graphite sheets. Since the discovery, the method has been receiving wide attention due to its unique electronic structure, large specific surface area, adjustable length-diameter ratio and other characteristics. However, since the carbon nanotubes are hydrophobic materials, the carbon nanotubes are difficult to wet in an aqueous solution, lack functional groups on the surface, and are difficult to be reduced by metal ions attached to the surface, the carbon nanotubes are often subjected to surface functionalization pretreatment in application. For example, the surface of the carbon nanotube is modified with groups such as hydroxyl, carboxyl, epoxy, etc. by soaking or refluxing with a strong oxidant (concentrated sulfuric acid, concentrated nitric acid, etc.); or through hydrothermal reaction in ammonia water, the surface of the carbon nano tube is modified with amino groups and other groups, and the carbon nano tube with the groups can be soaked in water and can well adsorb metal ions so that the metal is well dispersed on the surface of the carbon nano tube.
In the catalytic hydrazine hydrate reaction, the amino modification on the surface of the catalyst is beneficial to improving the catalytic reaction activity and catalytic selectivity, but the prior methods for surface amination are few, most of the existing methods are carried out in aqueous solution, and some reaction conditions are harsh, so that the method is not beneficial to large-scale industrial treatment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a supported catalyst which is used for preparing hydrogen by decomposing hydrazine hydrate and takes an amino-functionalized carbon nano tube as a carrier. The carbon nano tube is continuously heat treated by urea at a lower temperature to prepare the platinum or rhodium taking the carbon nano tube with the functionalized amino as a carrier and the supported catalyst of binary alloy of the platinum or rhodium and other metals. The preparation process is simple, and no strong acid, strong alkali and other polluting liquids exist. The carbon nano tube carrier after amino functionalization greatly improves the catalytic performance of platinum or rhodium and binary alloy of platinum or rhodium and other metals, the performance of decomposing and preparing hydrogen from hydrazine hydrate exceeds that of other commercial catalysts, and a high-efficiency catalyst material is provided for preparing hydrogen from industrial hydrazine hydrate by dehydrogenation.
The method of the invention comprises the following steps:
the method comprises the following steps: preparing an amino functionalized carbon nanotube carrier:
firstly, mixing a carbon nano tube with urea at room temperature, then carrying out heat treatment on the mixture for 2-3 hours at 275-350 ℃ in the air atmosphere, naturally cooling, washing the mixture for 3 times with water, then washing the mixture for 3 times with ethanol to remove unreacted impurities, and drying to obtain the carbon nano tube subjected to primary treatment; and mixing the carbon nano tube subjected to the primary treatment with urea again at room temperature, then carrying out heat treatment on the mixture for 3-5 hours at 150-200 ℃ in an air atmosphere, washing the mixture for 3 times with water, washing the mixture for 3 times with ethanol to remove unreacted impurities, and drying to obtain the amino-functionalized carbon nano tube carrier.
In the first step, the carbon nano tube is at least one selected from commercial single-wall carbon nano tube and commercial multi-wall carbon nano tube; the mass ratio of the carbon nano tube to the urea is 1: 1-3, such as: 1:1, 1:2, 1:3, and the like.
The prepared amino-functionalized carbon nano tube has amino-NH 2 Amide group-CONH 2 Functional groups and pyridine nitrogen doped into the carbon nanotube, but the carbon nanotube subjected to one-time treatment cannot simultaneously obtain the same effect regardless of the extension of the heat treatment time or the increase of the heat treatment temperature. Therefore, the nitrogen functionalized carbon nano tube carrier with special properties can be prepared by the optimized twice heat treatment process.
Step two: preparing a metal or alloy supported catalyst of amino functionalized carbon nano tube:
preparing the prepared amino functionalized carbon nano tube into 0.1-1 wt% of water solution, performing ultrasonic dispersion or stirring treatment for 5-60 minutes to form uniform solution, adding a platinum salt or rhodium salt and one of nickel salt and cobalt salt into the solution, and stirring for 5-60 minutes. The total mass fraction of the metal salt accounts for 1-10% of the mass of the amino functionalized carbon nano tube carrier. And 3-50 ml of sodium borohydride aqueous solution with the molar weight 5-10 times of the total molar weight of the metal salt is prepared to be used as a reducing agent solution, the reducing agent solution is added into the mixed solution of the amino functionalized carbon nanotube carrier and the metal salt at the temperature of 0-50 ℃, the reaction is carried out for 5-120 minutes at the temperature of 0-50 ℃, and the metal salt is reduced to metal particles. And centrifugally washing and vacuum drying to obtain the metal or alloy supported catalyst of the amino functionalized carbon nano tube.
In the second step, the platinum salt is selected from potassium chloroplatinate, sodium chloroplatinate, chloroplatinic acid and the like; the rhodium salt is selected from rhodium chloride, potassium chlororhodate and the like; the nickel salt is selected from nickel sulfate, nickel nitrate or nickel oxalate and the like; the cobalt salt is selected from cobalt chloride and the like.
Compared with the prior art, the invention has obvious positive effect and advancement: the carbon nano tube is treated by the solution method or the hydrothermal method adopted at present, only the carbon nano tube modified by single amino group can be obtained, the carbon nano tube treated by high-temperature atmosphere is the main method for preparing the nitrogen-doped carbon nano tube, the amino group with low thermal stability can not be reserved at high temperature, urea is selected as a nitrogen source, and the carbon nano tube treated by twice atmosphere can be prepared to have amino-NH 2 Amide group-CONH 2 The functional groups and the carbon nano tubes doped with the pyridine nitrogen and functionalized by various nitrogen enter the carbon nano tubes, when the carbon nano tubes are loaded with a metal catalyst, the reduced metal particles can be smaller in size and more uniform in distribution so as to obtain higher catalytic hydrazine hydrate dehydrogenation activity, and meanwhile, the special electronic structure of the functionalized carbon nano tubes can also improve the reaction selectivity of the catalytic hydrazine hydrate, so that the performance of the catalyst is higher than that of the existing catalysts.
The preparation method provided by the invention not only improves the controllability in the preparation process, but also has the advantages of simple process and easiness in realization, can efficiently catalyze the hydrogen production reaction by hydrazine hydrate decomposition, and greatly promotes the application of the hydrogen production by hydrazine hydrate decomposition.
Drawings
Fig. 1 is a transmission electron microscope image of an amino-functionalized carbon nanotube-supported PtNi alloy catalyst prepared in example 1 of the present invention.
Fig. 2 is an X-ray photoelectron spectrum of nitrogen in the PtNi alloy catalyst supported by amino-functionalized carbon nanotubes prepared in example 1 of the present invention.
Fig. 3 is a curve of the change of the molar weight of hydrazine hydrate to decompose hydrogen at different temperatures of PtNi alloy catalysts loaded on amino-functionalized carbon nanotubes prepared in examples 1 and 3 of the present invention with time.
Fig. 4 is a transmission electron microscope image of the amino-functionalized carbon nanotube-supported PtNi alloy catalyst prepared in example 1 of the present invention after repeated use.
Fig. 5 is a graph showing the change of the molar weight of hydrogen produced by decomposing hydrazine hydrate, which is repeatedly used five times, in the PtNi alloy catalyst supported by the amino-functionalized carbon nanotube prepared in example 1 of the present invention, over time.
Fig. 6 is a time-dependent change curve of the molar mass of hydrogen produced by decomposing hydrazine hydrate in the carbon nanotube-supported PtNi alloy catalyst prepared in example 4 of the present invention.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1: preparation of PtNi alloy catalyst loaded on amino functionalized carbon nano tube
The method comprises the following steps: preparing an amino functionalized carbon nanotube carrier:
grinding and mixing 1 g of carbon nano tube and 1.5 g of urea in a grinding kettle at room temperature, then carrying out heat treatment on the mixture for 2 hours at 300 ℃ in an air atmosphere, naturally cooling, washing the mixture for 3 times with water, then washing the mixture for 3 times with ethanol, removing unreacted impurities, and drying to obtain the carbon nano tube subjected to primary treatment; and grinding and mixing the once-treated 1 g of carbon nano tube and 2 g of urea in a grinding kettle again at room temperature, then carrying out heat treatment on the mixture for 4 hours at 175 ℃ in an air atmosphere, washing the mixture for 3 times with water, washing the mixture for 3 times with ethanol to remove unreacted impurities, and drying to obtain the amino-functionalized carbon nano tube carrier.
Step two: preparation of the PtNi alloy catalyst loaded by the amino functionalized carbon nano tube:
preparing 50ml of aqueous solution of 0.1 wt% of amino functionalized carbon nano tube, performing ultrasonic dispersion for 20 minutes to form uniform solution, adding 1.7 mg of potassium chloroplatinate and 2 mg of nickel chloride into the solution, and stirring for 30 minutes. And preparing 5 ml of aqueous solution containing 37 mg of sodium borohydride as a reducing agent solution, adding the reducing agent solution into the mixed solution of the amino-functionalized carbon nanotube carrier and the metal salt at the temperature of 25 ℃, reacting for 60 minutes at the temperature of 25 ℃, and carrying out centrifugal washing and vacuum drying to obtain the amino-functionalized carbon nanotube-loaded PtNi alloy catalyst.
Fig. 1 is a transmission electron microscope image of the PtNi alloy catalyst supported by amino-functionalized carbon nanotubes prepared in example 1 of the present invention, and it can be seen from the image that the particle size of the nickel-platinum catalyst does not exceed 3 nm. FIG. 2 is an X-ray photoelectron spectrum of nitrogen in the PtNi alloy catalyst supported by amino-functionalized carbon nanotubes prepared in example 1, and it can be seen from the graph that the amino-functionalized carbon nanotubes prepared in the present invention have amino groups-NH 2 Amide group-CONH 2 Functional groups and pyridine nitrogen doped into the carbon nanotubes.
Example 2: preparation of amino-functionalized carbon nanotube-loaded RhNi alloy catalyst
Preparation of amino-functionalized carbon nanotube Supports As in example 1
Preparing 50ml of aqueous solution of 0.1 wt% of amino-functionalized carbon nanotube, performing ultrasonic dispersion for 20 minutes to form uniform solution, adding 1 mg of rhodium trichloride and 1.5 mg of nickel chloride into the solution, and stirring for 30 minutes. And preparing 5 ml of aqueous solution containing 37 mg of sodium borohydride as a reducing agent solution, adding the reducing agent solution into the mixed solution of the amino-functionalized carbon nanotube carrier and the metal salt at the temperature of 25 ℃, reacting for 60 minutes at the temperature of 25 ℃, and carrying out centrifugal washing and vacuum drying to obtain the amino-functionalized carbon nanotube-loaded RhNi alloy catalyst.
Example 3: hydrazine hydrate (N) containing PtNi alloy catalyst loaded by amino functionalized carbon nano tube 2 H 4 ·H 2 O) hydrolysis hydrogen production system: the system comprises an amino-functionalized carbon nanotube-loaded PtNi alloy catalyst and hydrazine hydrate aqueous solution. The research on the hydrogen production by decomposing hydrazine hydrate in the system is as follows:
adding 50mg of prepared PtNi alloy catalyst loaded on amino-containing functionalized carbon nano tubes into a catalyst containing PtNi4ml of deionized water with 0.1mol/L of sodium hydroxide is put into a three-neck flask which is fixed in a water bath constant temperature oscillator, the reaction temperature can be adjusted by the water bath, the oscillator drives the three-neck flask to rotate and oscillate at 220 circles/minute, and 0.1ml of hydrazine hydrate (N) is added by a liquid-transferring gun 2 H 4 ·H 2 O), after adding, the three-mouth bottle is closed by a rubber plug, and immediately a stopwatch is pressed to start timing. The hydrogen generated was detected by Shimadzu DC-14C gas chromatography using a 0.5nm molecular sieve column (3 m.times.2 mm), thermal conductivity cell detector (TCD) and argon as carrier gas.
The effect of reaction temperature on the rate of catalytic hydrolysis in this system was investigated, comprising the following steps:
the temperature of the hydrazine hydrate hydrolysis hydrogen production system containing the amino-functionalized carbon nanotube-loaded PtNi alloy catalyst is 298K, 303K, 313K and 323K respectively. The volume of hydrogen collected at different times for each reaction was recorded. The time required for complete hydrogen release was 9.1min, 6min, 3.1min and 2.3min, respectively, with the hydrogen volume plotted against time, as shown in figure 3. In the system, the catalytic conversion rate of 1623h can be obtained at 323K by calculating the catalytic conversion rate -1 。
The method for researching the recycling condition of the catalyst in the system comprises the following steps:
after the first catalytic hydrazine hydrate hydrolysis hydrogen production reaction is finished, adding the same amount of hydrazine hydrate (0.1ml) into a three-necked bottle, and continuously measuring the hydrogen production rate of the catalyst. After the reaction is finished, the same amount of hydrazine hydrate is added again, and the cycle is repeated for 5 times. The hydrogen yield to hydrazine hydrate ratio and the corresponding reaction time were recorded for each re-use. From the results shown in fig. 5, it can be concluded that the amino-functionalized carbon nanotube-supported PtNi alloy catalyst maintains high activity for catalyzing the hydrolysis of hydrazine hydrate to produce hydrogen. The catalyst recovered after the cycling reaction was analyzed by transmission electron microscopy as shown in fig. 4. It can be seen from the figure that there is no significant change in the morphology of the catalyst after the reaction, i.e., the catalyst can be stably present after the cycling reaction.
Example 4: preparation of carbon nano tube loaded PtNi alloy catalyst
Preparing a 0.1 wt% mass fraction of commercial carbon nanotube into 50ml of aqueous solution, performing ultrasonic dispersion for 20 minutes to form a uniform solution, adding 1.7 mg of potassium chloroplatinate and 2 mg of nickel chloride into the solution, and stirring for 30 minutes. And preparing 5 ml of aqueous solution containing 37 mg of sodium borohydride as a reducing agent solution, adding the reducing agent solution into the mixed solution of the amino-functionalized carbon nanotube carrier and the metal salt at the temperature of 25 ℃, reacting for 60 minutes at the temperature of 25 ℃, and carrying out centrifugal washing and vacuum drying to obtain the carbon nanotube-loaded PtNi alloy catalyst.
Fig. 6 is a curve of the change of the molar mass of the carbon nanotube-supported PtNi alloy catalyst hydrazine hydrate prepared in example 4 with time to decompose hydrogen. As can be seen from the figure, the carbon nanotube-supported PtNi alloy catalyst which is not subjected to the nitrogen functionalization treatment of the present invention has lower hydrazine hydrate catalytic activity, which indicates that the hydrazine hydrate hydrogen production performance of the carbon nanotube-supported catalyst subjected to the nitrogen functionalization treatment prepared by the present invention is better than that of the catalyst subjected to the nitrogen functionalization treatment.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.
Claims (4)
1. A preparation method of hydrazine hydrate dehydrogenation catalyst is characterized in that urea is adopted to carry out heat treatment on carbon nano tubes continuously for two times at a lower temperature to prepare amino-functionalized carbon nano tube carriers, sodium borohydride is further used as a reducing agent to reduce binary alloy formed by platinum salt or rhodium salt and other metal salts to be loaded on the amino-functionalized carbon nano tube carriers to synthesize the supported catalyst taking the amino-functionalized carbon nano tubes as the carriers, and the preparation method comprises the following steps:
1) firstly, mixing a carbon nano tube with urea at room temperature, then carrying out heat treatment on the mixture for 2-3 hours at 275-350 ℃ in the air atmosphere, naturally cooling, washing the mixture for 3 times with water, then washing the mixture for 3 times with ethanol to remove unreacted impurities, and drying to obtain the carbon nano tube subjected to primary treatment; and mixing the carbon nano tube subjected to the primary treatment with urea again at room temperature, then carrying out heat treatment on the mixture for 3-5 hours at 150-200 ℃ in an air atmosphere, washing the mixture for 3 times, then washing the mixture for 3 times with ethanol to remove unreacted impurities, and drying to obtain the amino functionalized carbon nano tube carrier.
2) Preparing an amino functionalized carbon nano tube into 0.1-1 wt% of aqueous solution, performing ultrasonic dispersion or stirring treatment for 5-60 minutes to form a uniform solution, adding one of platinum salt or rhodium salt and nickel salt and cobalt salt into the solution, and stirring for 5-60 minutes. The total mass fraction of the metal salt accounts for 1-10% of the mass of the amino functionalized carbon nano tube carrier. And preparing 3-50 ml of sodium borohydride aqueous solution with the molar weight 5-10 times of the total molar weight of the metal salt as a reducing agent solution, adding the reducing agent solution into the mixed solution of the amino functionalized carbon nanotube carrier and the metal salt at the temperature of 0-50 ℃, reacting for 5-120 minutes at the temperature of 0-50 ℃, and reducing the metal salt to metal particles. And (3) centrifugally washing, and drying in vacuum to obtain the metal supported catalyst with the amino functionalized carbon nano tube as the carrier.
2. The carbon nanotube of claim 1 is at least one selected from the group consisting of a commercial single-walled carbon nanotube and a commercial multi-walled carbon nanotube; the mass ratio of the carbon nano tube to the urea is 1: 1-3.
3. A method for preparing a hydrazine hydrate dehydrogenation catalyst according to claim 1, characterized in that: the platinum salt is selected from potassium chloroplatinate, sodium chloroplatinate, chloroplatinic acid and the like; the rhodium salt is selected from rhodium chloride, potassium chlororhodate and the like; the nickel salt is selected from nickel sulfate, nickel nitrate or nickel oxalate and the like; the cobalt salt is selected from cobalt chloride and the like.
4. The application of the metal supported catalyst with the amino functionalized carbon nano tube as the carrier according to claim 1 in hydrogen production through decomposition of hydrazine hydrate.
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