CN115254141B - Micro-noble metal supported catalyst, preparation method and application thereof - Google Patents
Micro-noble metal supported catalyst, preparation method and application thereof Download PDFInfo
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- CN115254141B CN115254141B CN202211048739.0A CN202211048739A CN115254141B CN 115254141 B CN115254141 B CN 115254141B CN 202211048739 A CN202211048739 A CN 202211048739A CN 115254141 B CN115254141 B CN 115254141B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 abstract description 20
- 238000003860 storage Methods 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 14
- 239000002131 composite material Substances 0.000 abstract description 12
- 150000003303 ruthenium Chemical class 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- -1 ruthenium ions Chemical class 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 19
- 229910000943 NiAl Inorganic materials 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000002905 metal composite material Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 230000003993 interaction Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 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 description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 6
- 150000002815 nickel Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012050 conventional carrier Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/007—Mixed salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a micro noble metal supported catalyst, a preparation method and application thereof, and relates to the technical field of preparation of hydrogenation catalysts. The method comprises the following steps: preparing a NiAl-type bimetal composite nano hydroxide and a NiAl-type bimetal composite nano oxide carrier precursor, adding the prepared carrier precursor into a ruthenium salt aqueous solution, stirring at normal temperature for a period of time, sequentially centrifuging, washing, drying, reducing by high-temperature hydrogen, and grinding into powder to obtain the high-performance hydrogenation catalyst, wherein the mass of ruthenium ions contained in the ruthenium salt aqueous solution is 0.5% -2% of that of the carrier precursor. The catalyst prepared by the invention can realize 100% conversion rate of the nitrogen heterocyclic organic liquid hydrogen storage carrier substrate and selectivity of aromatic ring full hydrogenation products of more than 99%, achieves the effect of even more than part of high-load commercial noble metal catalysts under the condition of using trace noble metals, and is obviously superior to other micro noble metal load catalysts.
Description
Technical Field
The invention relates to the technical field of preparation of hydrogenation catalysts, in particular to a micro-noble metal loaded high-performance hydrogenation catalyst, a preparation method and application thereof.
Background
In 1975, sultan and Shaw proposed for the first time the use of liquid unsaturated organics for hydrogen storage, after which liquid organics hydrogen storage developed rapidly as a novel hydrogen storage technology. The technical principle is that the hydrogen storage is realized by utilizing the catalytic addition of organic molecular unsaturated bonds and hydrogen, and the hydrogen is released again by changing the reverse reaction of conditions; or coupled with other industrial processes, and reforms hydrogen production from the product of the process, thereby realizing the function of hydrogen storage. The organic liquid hydrogen storage technology has the advantages of higher hydrogen storage density, multiple circulation, convenient transportation, available existing energy network and the like, and is one of the most potential hydrogen storage technologies. From the viewpoint of technology reserve diversification, the organic liquid hydrogen storage technology is worth being put into practice.
However, in the prior art, some problems restricting further application and popularization of the organic liquid hydrogen storage technology still exist, and the difficulty in compatibility of the catalyst cost and efficiency in the hydrogenation process is one of the problems. At present, most of catalysts commonly used in hydrogenation processes of organic liquid hydrogen storage technology are Ru-based noble metal catalysts with alumina or activated carbon as carriers and load of 5-10%, and the cost is high; while less expensive non-noble metal catalysts (e.g., ni-based catalysts) have lower hydrogenation efficiency.
Therefore, how to reduce the cost and ensure the higher activity of the hydrogenation catalyst at the same time has attracted attention of researchers in the field.
Disclosure of Invention
The invention aims to provide a preparation method of a micro noble metal supported catalyst, which reduces the cost by reducing the noble metal supported amount, and regulates and controls the particle size of a noble metal Ru nano cluster supported by changing the structure of a carrier, so that the utilization rate of noble metal particles is improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the micro noble metal supported catalyst sequentially comprises the following steps:
a. preparing a precursor of a NiAl-based bimetal composite nano hydroxide carrier and a precursor of a NiAl-based bimetal composite nano oxide carrier, which comprises the following substeps:
a1, selecting raw materials of nickel salt, aluminum salt, ruthenium salt, ethanol and deionized water, and co-dissolving the nickel salt and the aluminum salt in the ethanol and the deionized water according to the mass ratio of 0.2-5 to obtain a mixed solution;
a2, placing the mixed solution in a high-pressure hydrothermal reaction kettle, wherein the high-pressure hydrothermal reaction kettle is provided with a stirring device and a temperature control device, heating the mixed solution to 120-160 ℃ and keeping the temperature for 10-12 h, then starting the stirring device, and raising the temperature of the mixed solution to 150-260 ℃ again under the stirring state;
a3, stopping heating and stirring, cooling the mixed solution to room temperature, centrifuging the obtained powder, washing for several times by water and an organic solvent in sequence, drying for 10-14 h, and grinding the obtained product into powder to obtain the NiAl bimetallic composite nano hydroxide carrier precursor;
a4, calcining part of the precursor of the NiAl-based bimetal composite nano hydroxide carrier in the step a3 at 600-800 ℃ to obtain the precursor of the NiAl-based bimetal composite nano oxide carrier;
b. adding the precursor of the NiAl-based double-metal composite nano hydroxide carrier obtained in the step a3 or the precursor of the NiAl-based double-metal composite nano oxide carrier obtained in the step a4 into ruthenium salt aqueous solution, stirring at normal temperature for a period of time, centrifuging, washing, drying, reducing with hydrogen, and grinding into powder to obtain the micro-noble metal supported catalyst, wherein the mass of ruthenium ions contained in the ruthenium salt aqueous solution is 0.5% -2% of that of the corresponding carrier precursor.
In a preferred embodiment of the present invention, in step a1, the nickel salt includes nickel nitrate and nickel acetylacetonate.
As another preferred embodiment of the present invention, in step a1, the aluminum salt includes aluminum nitrate, aluminum isopropoxide or aluminum acetylacetonate.
Further, in step a1, the ruthenium salt includes ruthenium trichloride or ruthenium acetylacetonate.
Further, in step a2, the rotation speed of the stirring device is 400 to 600 rpm.
In step a3, deionized water is selected for washing, and ethanol is used for washing for a plurality of times.
Further, the mass of ruthenium ions is 0.5% -2% of the mass of the carrier precursor.
Further, in step a2, the mixing heating time is 0.1 to 10 hours, and in step a4, the calcining time is 0.1 to 5 hours.
The invention also aims to provide the micro-noble metal supported catalyst prepared by the preparation method of the micro-noble metal supported catalyst.
It is still another object of the present invention to provide the use of the above-mentioned micro noble metal supported catalyst in a batch hydrogenation reaction of N-ethylcarbazole, wherein the reaction pressure is 8MPa and the reaction temperature is 150 ℃.
The reaction mechanism of the invention is as follows:
the invention selects nickel salt and aluminum salt with relatively low price to prepare NiAl-like bimetal composite nano hydroxide carrier precursor and NiAl-like bimetal composite nano oxide carrier precursor by self, and carries noble metal, then carries Ru by high-temperature hydrogen reduction 3+ When the nickel-aluminum composite nano-oxide is reduced into Ru nano-particles, the precursor of the NiAl-like double-metal composite nano-hydroxide/oxide carrier is heated to generate the NiAl-like double-metal composite nano-oxide carrier, and the porosity, specific surface area, surface electron cloud density and crystal defects of the NiAl-like double-metal composite nano-oxide carrier finally generated can be regulated and controlled by changing the raw material ratio and preparation conditions of the nickel-aluminum. Specifically, the composition of the NiAl layered double metal composite nano oxide can be changed by changing the roasting temperature and the roasting time of the raw materials, and the NiAl interaction in the NiAl layered double metal composite nano oxide gradually becomes stronger along with the rising of the roasting temperature and the extension of the roasting time, and the NiAl interaction is formed by NiO-Al 2 O 3 The strong interaction gradually changes into NiAl 2 O 4 Extremely strong interactions with NiAl; the composition of the finally generated NiAl layered double metal composite nano oxide can be changed by changing the NiAl ratio of the raw material, thereby affecting NiO-Al 2 O 3 Strong and weak interaction and possibility of NiO-NiAl generation 2 O 4 Very weak interactions. The interaction of the bimetallic composite oxides among the carriers is different, so that direct influence can be generated on the surface electron cloud density and crystal defects of the carriers, the nanometer particle size of ruthenium clusters obtained through reduction can be regulated and controlled, the utilization rate of noble metal ruthenium is improved, and the catalytic performance is improved. It is known that the smaller the particle size of the active metal of the supported catalyst, the higher the utilization of the active metal, and the higher the catalytic activity of the catalyst. The special surface environment of the carrier is favorable for the active metal Ru 3+ Is dispersed and adsorbed to makeThe particle size of the Ru nano-particles is very small. The catalyst can realize better catalytic effect by combining the functions of high specific surface area of the carrier and small particle size of ruthenium clusters, and reducing the load of noble metal ruthenium (the mass of ruthenium ions contained in ruthenium salt aqueous solution is 0.5-2% of that of the NiAl bimetallic composite nano-oxide carrier).
Compared with the prior art, the invention has the following beneficial technical effects:
(1) According to the invention, by selecting noble metal ruthenium with micro-loading (0.5% -2%) and combining with improvement of the carrier, the hydrogenation catalyst with small loading and high catalytic activity can be realized.
(2) The preparation method is simple, and the related preparation methods have mature industrialized application cases and have no complex and high-value production equipment requirements.
(3) The preparation method has the advantages of mild preparation conditions, low energy consumption and easy industrial popularization.
(4) The carrier used in the invention has the advantages of easily available raw materials, extremely low noble metal loading dosage and further reduced cost.
(5) The catalyst disclosed by the invention has good active metal dispersibility, and the noble metal utilization rate is greatly improved. In addition, the method does not use additives such as surfactants which are difficult to post-treat to assist the dispersion and molding of the active metal, and good dispersibility can be obtained.
(6) The catalyst has extremely high catalytic activity, and can ensure that the hydrogenation conversion rate and the selectivity of the nitrogen heterocyclic organic liquid hydrogen storage carrier are more than 98 percent and more than 90 percent within 1 hour.
The micro noble metal loaded catalyst prepared by the method of the invention effectively reduces the cost, ensures higher catalytic activity, is suitable for mass production, solves the problem that the catalyst efficiency and the cost cannot be considered in the application field of organic liquid hydrogen storage to a certain extent, and can be popularized and applied.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a TEM image of a hydrogenation catalyst prepared according to example 1 of the present invention;
FIG. 2 is an SEM image of a hydrogenation catalyst prepared according to example 1 of the invention;
FIG. 3 is a graph showing the hydrogenation activity of comparative examples 1 and 2;
FIG. 4 is a diagram showing structural characterization of the carrier precursor and the carrier prepared in example 1 of the present invention.
Detailed Description
The invention provides a high-performance hydrogenation catalyst, a preparation method and application thereof, and in order to make the advantages and the technical scheme of the invention clearer and more definite, the invention is further described below by combining specific embodiments.
The raw materials used in the present invention are all commercially available.
The nickel salts mentioned in the present invention include nickel nitrate and nickel acetylacetonate; the nickel nitrate refers to nickel nitrate hexahydrate.
The aluminum salts mentioned in the present invention include aluminum nitrate, aluminum isopropoxide or aluminum acetylacetonate; the aluminum nitrate refers to aluminum nitrate nonahydrate.
Ruthenium salts described in the present invention include ruthenium trichloride or ruthenium acetylacetonate.
Depending on the kind of the above nickel salt, aluminum salt and ruthenium salt, the following different combinations are possible.
Combining: nickel nitrate, aluminum nitrate, ruthenium trichloride;
and (2) combining two: nickel nitrate, aluminum isopropoxide, ruthenium trichloride;
and (3) combining three: nickel nitrate, aluminum acetylacetonate, ruthenium acetylacetonate;
combining nickel nitrate, aluminum nitrate and ruthenium acetylacetonate;
other combinations of embodiments will be apparent to those skilled in the art upon review of the foregoing description.
The preparation method of the high performance hydrogenation catalyst of the present invention will be described in detail with reference to examples.
Example 1:
the preparation method of the micro noble metal supported catalyst comprises the following steps:
weighing 2.91g of nickel nitrate hexahydrate and 7.50g of aluminum nitrate nonahydrate, and co-dissolving the nickel nitrate hexahydrate and the aluminum nitrate nonahydrate in a proper amount of deionized water to obtain a solution I; weighing 12g of urea, and dissolving the urea in a proper amount of water to obtain a solution II;
and step two, mixing the solution I and the solution II, pouring the mixture into a high-pressure hydrothermal reaction kettle, heating the mixture to 120 ℃ for hydrothermal reaction for 12 hours, and stopping heating. After cooling to room temperature, the powder was centrifuged, washed several times with deionized water and ethanol, and then dried at 100 ℃ for 12 hours. The resulting support product was ground to a powder.
Step three, 1g of the powdery solid is taken and added into ruthenium trichloride aqueous solution (containing Ru) 3+ 0.015 g), stirring at a low rotating speed for 24 hours at normal temperature, centrifuging, washing, drying, reducing with 400 ℃ hydrogen for 3 hours, and grinding into powder to obtain the noble metal Ru-based high-performance hydrogenation catalyst.
The hydrogenation catalyst prepared in the embodiment is subjected to intermittent hydrogenation reaction of N-ethyl carbazole at 8MPa and 150 ℃, the conversion rate of N-ethyl carbazole after one hour of reaction is 100%, and the selectivity of the total hydrogenation product dodecahydro-N-ethyl carbazole is 100%.
The XRD pattern of the carrier precursor and the carrier prepared in step two of example 1 of the present invention is shown in fig. 4, and it can be seen from fig. 4: the support precursor of example 1 is NiAl-based bimetallic hydroxide, and the support of example 1 is NiO crystal and amorphous Al 2 O 3 Is a mixture of (a) and (b).
Example 2:
the preparation method of the micro noble metal supported catalyst comprises the following steps:
weighing 5.82g of nickel nitrate hexahydrate and 3.75g of aluminum nitrate nonahydrate, and co-dissolving the nickel nitrate hexahydrate and the aluminum nitrate nonahydrate in a proper amount of deionized water to obtain a solution I; weighing 12g of urea, and dissolving the urea in a proper amount of water to obtain a solution II;
and step two, mixing the solution I and the solution II, pouring the mixture into a high-pressure hydrothermal reaction kettle, heating the mixture to 120 ℃ for hydrothermal reaction for 12 hours, and stopping heating. After cooling to room temperature, the powder was centrifuged, washed several times with deionized water and ethanol, and then dried at 100 ℃ for 12 hours. The resulting support product was ground to a powder.
Step three, 1g of the powdery solid is taken and added into ruthenium trichloride aqueous solution (containing Ru) 3+ 0.015 g), stirring at a low rotating speed for 24 hours at normal temperature, centrifuging, washing, drying, reducing with 400 ℃ hydrogen for 3 hours, and grinding into powder to obtain the noble metal Ru-based high-performance hydrogenation catalyst.
The high-performance hydrogenation catalyst prepared in the embodiment is subjected to N-ethyl carbazole intermittent hydrogenation reaction at 8MPa and 150 ℃, the conversion rate of N-ethyl carbazole after one hour of reaction is 100%, and the selectivity of the full hydrogenation product dodecahydro-N-ethyl carbazole is 99.43%.
Example 3:
the preparation method of the micro noble metal supported catalyst comprises the following steps:
weighing 5.82g of nickel nitrate hexahydrate and 3.75g of aluminum nitrate nonahydrate, and co-dissolving the nickel nitrate hexahydrate and the aluminum nitrate nonahydrate in a proper amount of deionized water to obtain a solution I; weighing 12g of urea, and dissolving the urea in a proper amount of water to obtain a solution II;
and step two, mixing the solution I and the solution II, pouring the mixture into a high-pressure hydrothermal reaction kettle, heating the mixture to 120 ℃ for hydrothermal reaction for 12 hours, and stopping heating. After cooling to room temperature, the powder was centrifuged, washed several times with deionized water and ethanol, then dried at 100 ℃ for 12 hours and calcined at 700 ℃ for 5 hours. The resulting support product was ground to a powder.
Step three, 1g of the powdery solid is taken and added into ruthenium trichloride aqueous solution (containing Ru) 3+ 0.015 g), stirring at a low rotating speed for 24 hours at normal temperature, centrifuging, washing, drying, reducing with 400 ℃ hydrogen for 3 hours, and grinding into powder to obtain the noble metal Ru-based high-performance hydrogenation catalyst.
The high-performance hydrogenation catalyst prepared in the embodiment is subjected to N-ethyl carbazole intermittent hydrogenation reaction at 8MPa and 150 ℃, the conversion rate of N-ethyl carbazole after one hour of reaction is 93.36%, and the selectivity of the full hydrogenation product dodecahydro-N-ethyl carbazole is 72.30%.
Example 4:
the preparation method of the micro noble metal supported catalyst comprises the following steps:
step one, weighing 7.71g of nickel acetylacetonate and 3.06g of aluminum isopropoxide, dissolving in 50ml of ethanol altogether, and sealing in a 100 ml autoclave;
and step two, heating the mixture obtained in the step one to 120 ℃ and keeping the temperature for 10 hours, then raising the temperature to 160 ℃ and keeping the temperature for 10 hours under the continuous stirring of 500 revolutions per minute, stopping heating and stirring, cooling the mixture to room temperature, centrifuging the powder product, washing the powder product with deionized water and ethanol for several times, drying the powder product at 100 ℃ for 12 hours, and finally calcining the powder product at 700 ℃ for 5 hours in a muffle furnace.
And thirdly, grinding the product obtained in the second step into powder. 1g of the above powdery solid was taken and added to an aqueous ruthenium trichloride solution (containing Ru 3+ 0.0075 g), stirring at a low speed for 24 hours at normal temperature, centrifuging, washing, drying, roasting with hydrogen at 400 ℃ for 3 hours, and grinding into powder to obtain the noble metal Ru-based high-performance hydrogenation catalyst.
The high-performance hydrogenation catalyst prepared in the embodiment is subjected to N-ethyl carbazole intermittent hydrogenation reaction at 8MPa and 150 ℃, the conversion rate of N-ethyl carbazole after one hour of reaction is 99.08%, and the selectivity of the full hydrogenation product dodecahydro-N-ethyl carbazole is 72.76%.
Comparative example 1:
the difference from example 1 is that comparative example 1 uses a conventional carrier to support the micro noble metal Ru.
The method specifically comprises the following steps:
step one, adding 20mL of water into 1g of titanium dioxide (P25 type), and stirring until the water is uniformly dispersed to obtain an active carbon dispersion liquid;
step two, adding a proper amount of ruthenium trichloride solution (containing Ru) into the active carbon dispersion liquid 3+ 0.02 g), stirring at normal temperature and low speed for 24 hours, vacuum drying the stirred mixed solution at 60 ℃ for 16 hours, and grinding the obtained product into powder;
step three, the catalyst powder containing the precursor obtained in the step two is subjected to reduction treatment, and hydrogen is generated for 3 hours at 400 ℃ to obtain 2 percentRu-TiO 2 The catalyst was used as a comparative hydrogenation catalyst.
The catalyst prepared in the embodiment is subjected to intermittent hydrogenation reaction of N-ethyl carbazole at 8MPa and 150 ℃, the conversion rate of N-ethyl carbazole after one hour of reaction is 100%, and the selectivity of the full hydrogenation product dodecahydro-N-ethyl carbazole is 62.54%.
Comparative example 2:
the difference from example 1 is that comparative example 2 uses a conventional carrier to support the noble metal amount Ru.
The method specifically comprises the following steps:
step one, adding 25mL of water into 1g of activated carbon, and stirring until the water is uniformly dispersed to obtain an activated carbon dispersion liquid;
step two, adding a proper amount of ruthenium trichloride solution (containing Ru) into the active carbon dispersion liquid 3+ 0.05 g), stirring at normal temperature and low speed for 24 hours, vacuum drying the stirred mixed solution at 60 ℃ for 12 hours, and grinding the obtained product into powder;
and thirdly, reducing the catalyst powder containing the precursor obtained in the step two for 3 hours at 400 ℃ with hydrogen, and obtaining the 5% Ru-C catalyst serving as a comparative hydrogenation catalyst.
The catalyst is subjected to N-ethyl carbazole intermittent hydrogenation reaction at 8MPa and 150 ℃, the conversion rate of N-ethyl carbazole after the reaction is carried out for 1 hour is 100%, and the selectivity of the total hydrogenation product dodecahydro-N-ethyl carbazole is 98.17%.
In summary, the micro-noble metal supported catalyst, the preparation method and the application thereof provided by the invention can realize 100% conversion rate of the nitrogen heterocyclic organic liquid hydrogen storage carrier substrate and selectivity of over 99% of aromatic ring full hydrogenation products, and achieve or even exceed partial high-supported commercial noble metal supported catalyst effect under the condition of using micro-noble metal, and are obviously superior to other micro-noble metal supported catalysts; the preparation method is simple and convenient, has mild preparation conditions, is easy to operate and low in cost, and is particularly suitable for large-scale production and industrial application.
The above examples 1 to 4 further illustrate the preparation method of the high performance catalyst of the present invention, but are not limited thereto, and other combinations of the preparation methods of the high performance catalyst may be obviously realized by those skilled in the art under the guidance of the above examples.
The parts not described in the invention can be realized by referring to the prior art.
It is noted that any equivalent or obvious modification made by those skilled in the art under the teachings of this specification shall fall within the scope of this invention.
Claims (1)
1. The application of the micro noble metal supported catalyst in the N-ethyl carbazole intermittent hydrogenation reaction is characterized in that the preparation method of the micro noble metal supported catalyst sequentially comprises the following steps:
weighing 2.91g of nickel nitrate hexahydrate and 7.50g of aluminum nitrate nonahydrate, and co-dissolving the nickel nitrate hexahydrate and the aluminum nitrate nonahydrate in a proper amount of deionized water to obtain a solution I; weighing 12g of urea, and dissolving the urea in a proper amount of water to obtain a solution II;
step two, mixing the solution I and the solution II, pouring the mixture into a high-pressure hydrothermal reaction kettle, heating the mixture to 120 ℃ for hydrothermal reaction for 12 hours, and stopping heating; after cooling to room temperature, the powder is centrifuged, washed with deionized water and ethanol for several times, and then dried at 100 ℃ for 12 hours, and the obtained carrier product is ground into powder;
step three, taking 1g of the powdery solid, and adding the powdery solid into a ruthenium trichloride aqueous solution, wherein the ruthenium trichloride aqueous solution contains Ru 3 + 0.015g, stirring at a low rotating speed for 24 hours at normal temperature, centrifuging, washing, drying, reducing for 3 hours by hydrogen at 400 ℃, and grinding into powder to obtain a micro noble metal supported catalyst;
the reaction pressure of the micro noble metal supported catalyst in the N-ethyl carbazole intermittent hydrogenation reaction is 8MPa, and the reaction temperature is 150 ℃.
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