CN114471651A - Supported catalyst and preparation method and application thereof - Google Patents
Supported catalyst and preparation method and application thereof Download PDFInfo
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- CN114471651A CN114471651A CN202011158799.9A CN202011158799A CN114471651A CN 114471651 A CN114471651 A CN 114471651A CN 202011158799 A CN202011158799 A CN 202011158799A CN 114471651 A CN114471651 A CN 114471651A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 118
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 48
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 57
- 239000011159 matrix material Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 39
- 239000002243 precursor Substances 0.000 claims description 34
- 229920000642 polymer Polymers 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 18
- 230000002829 reductive effect Effects 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- 125000002883 imidazolyl group Chemical group 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 87
- 239000007787 solid Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000001914 filtration Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 8
- 238000002955 isolation Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 2
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 2
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 2
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 108091006231 SLC7A2 Proteins 0.000 description 2
- 108091006230 SLC7A3 Proteins 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- 102100029272 5-demethoxyubiquinone hydroxylase, mitochondrial Human genes 0.000 description 1
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 1
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 1
- 101000770593 Homo sapiens 5-demethoxyubiquinone hydroxylase, mitochondrial Proteins 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- -1 nickel salt Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000004580 weight loss Effects 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
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Chemical & Material Sciences (AREA)
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- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention belongs to the technical field of catalysts, and discloses a supported catalyst, and a preparation method and application thereof. The supported catalyst comprises a substrate and ruthenium supported on the substrate, wherein the substrate comprises nitrogen-doped support carbon and nickel, and at least part of the nickel forms coordination bonds with lone-pair electrons on the nitrogen. The supported catalyst has the advantages of high catalytic activity and the like.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a supported catalyst and a preparation method and application thereof.
Background
The noble metal catalyst is a noble metal material which can change the chemical reaction speed and does not participate in the final reaction product. The most common noble metal catalysts in industry are supported platinum (Pd) and palladium (Pt) catalysts. In addition, supported ruthenium (Ru) noble metal catalysts are also used industrially, for example, in low-temperature methanation reactions and the like. Compared with other noble metal catalysts, the supported Ru catalyst has relatively low price and good industrial application prospect.
In literature reports, research on supported Ru catalysts mainly focuses on catalyst preparation and application, and catalysts suitable for hydrogenation or dehydrogenation reactions are usually obtained by using different carriers, different Ru precursors, different preparation methods, and the like. For example, an alumina-supported Ru catalyst is obtained by an impregnation method using an alumina carrier; obtaining a coconut shell carbon loaded Ru catalyst by using a coconut shell carbon carrier through an impregnation method; the titanium dioxide supported Ru catalyst is obtained by using a titanium dioxide carrier through methods of dipping, spraying and the like, and all the supported Ru catalysts can be used for reactions such as hydrogenation and the like. However, the supported Ru catalyst has problems of low noble metal utilization efficiency, low reactivity, low reaction stability, and the like due to the preparation method, composition, structure, and the like.
Therefore, it is necessary to develop a highly active Ru catalyst capable of improving the utilization rate of the noble metal Ru.
Disclosure of Invention
The invention aims to provide a supported catalyst, a preparation method and application thereof.
In a first aspect, the present invention provides a supported catalyst comprising a substrate and ruthenium supported thereon, wherein the substrate comprises nitrogen-doped support carbon and nickel, and at least a portion of the nickel forms coordination bonds with lone-pair electrons on the nitrogen.
In a second aspect, the present invention provides a method for preparing a supported catalyst, the method comprising:
1) dropwise adding the alcohol solution of the nickel precursor into the alcohol solution of the polymer containing the imidazole side group to perform a coordination reaction to obtain a reaction product of the polymer containing the imidazole side group and a complex of the nickel precursor;
2) separating the reaction product to obtain the complex serving as a high-molecular carrier;
3) carbonizing the polymer carrier to produce nitrogen-doped carrier carbon combined with nickel oxide;
4) carrying out hydrotreating on the carrier carbon in the step 3) to obtain a reduced matrix;
5) and (3) contacting the aqueous solution of the ruthenium precursor with the reduced substrate, and loading ruthenium on the substrate through adsorption and displacement reaction to obtain the supported catalyst.
In a third aspect, the present invention provides a supported catalyst prepared by the method of the second aspect of the present invention.
In a fourth aspect, the invention provides the use of the supported catalyst in hydrogenation reactions.
The supported catalyst provided by the invention is a supported Ru catalyst, which does not contain a traditional oxide or active carbon carrier, and is characterized in that nitrogen-doped carrier carbon obtained by high-molecular carbonization is combined with nickel as a matrix, coordination bonds exist between nitrogen and metallic nickel in the matrix, so that the metallic nickel is more uniformly dispersed, and the valence electronic structure is changed due to the coordination bonds, and the catalyst has the advantages of high catalytic activity, good selectivity, good stability and the like by combining with ruthenium. In addition, in the preparation method provided by the invention, the whole process can be carried out under the oxygen-free condition, and the operation of high-temperature roasting of the ruthenium-containing precursor under the oxygen-containing atmosphere in the traditional ruthenium catalyst preparation process can be avoided, so that the problem of emission of nitrogen oxides or chlorides caused by the traditional method is also avoided.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a supported catalyst comprising a substrate and ruthenium (Ru) supported thereon.
In the present invention, the matrix comprises nitrogen-doped support carbon and nickel, and at least a portion of the nickel (Ni) forms coordination bonds with lone-pair electrons on nitrogen (N). Specifically, the matrix comprises an in-situ generated nitrogen-containing carbon support and nickel coordinately loaded on the carbon support.
In the present invention, the matrix may be formed by carbonizing a polymer carrier. Wherein the macromolecular carrier is a complex of a polymer containing imidazole side groups and a nickel precursor (nickel salt). In the high molecular carrier, coordination bonds are formed between nickel and lone-pair electrons on nitrogen atoms in imidazole side groups, after high-temperature carbonization, the polymer is dehydrogenated and weightlessly to form carbon, nitrogen elements on imidazole groups of the polymer partially remain due to the coordination with nickel, and then a nitrogen-doped carbon material is formed, and nickel salt is decomposed by utilizing the high temperature of carbonization, so that nickel-containing element products such as nickel oxide, nickel simple substances and the like can be generated. In the matrix, nitrogen in the carrier carbon can be combined with nickel by a coordinate bond, so that the nickel is dispersed more uniformly.
In the invention, in the polymer containing the imidazole side group, the molecular chain of the polymer contains a repeating structural unit, and each repeating unit can contain an imidazole group so as to form a side chain of the whole molecule. The imidazole side group-containing polymer of the present invention is not particularly limited as long as a carbon support can be formed by carbonization. Preferably, the polymer containing pendant imidazole groups is selected from polyvinylimidazole or a copolymer of vinylimidazole and divinylbenzene. According to one embodiment, the polymer containing pendant imidazole groups is polyvinylimidazole. The polyvinylimidazoles can be prepared by methods known in the art (for example by free-radical polymerization using AIBN as initiator) or they can be obtained commercially. Generally, the polymerization degree (Xn) of the polyvinylimidazole may be 1000 to 10000. For example, AIBN is used as an initiator and toluene is used as a solvent, and the reaction is carried out in a hydrothermal kettle at 60 ℃ to obtain the polyvinyl imidazole with the Xn of 2000.
In the invention, in the supported catalyst, the weight ratio of the matrix to the ruthenium content is 100 to (0.01-1.0), preferably 100 to (0.1-1.0); the nickel content in the matrix is 10-60 wt%, preferably 45-60 wt%. The ruthenium content was calculated from the charge and the nickel content was determined by X-ray fluorescence spectroscopy (XRF) analysis.
According to a second aspect of the present invention, there is provided a process for the preparation of a supported catalyst, the process comprising:
1) dropwise adding the alcohol solution of the nickel precursor into the alcohol solution of the polymer containing the imidazole side group for coordination reaction to obtain a reaction product of the polymer containing the imidazole side group and the complex of the nickel precursor;
2) separating the reaction product to obtain the complex serving as a high-molecular carrier;
3) carbonizing the polymer carrier to produce nitrogen-doped carrier carbon combined with nickel oxide;
4) carrying out hydrotreating on the carrier carbon in the step 3) to obtain a reduced matrix;
5) and (3) contacting the aqueous solution of the ruthenium precursor with the reduced substrate, and loading ruthenium on the substrate through adsorption and displacement reaction to obtain the supported catalyst.
In the present invention, the purpose of step 1) is to coordinate and combine the nickel precursor with the imidazole group in the polymer to generate the complex of the polymer containing the imidazole side group and the nickel precursor. The coordination reaction is carried out under stirring conditions, and the stirring conditions comprise: the stirring speed is 50-600 rpm, preferably 200-400 rpm; the stirring time is 0.5 to 12 hours, preferably 3 to 8 hours.
The alcohol solvent is not particularly limited in the present invention, as long as it can form a homogeneous solution with the nickel precursor and can dissolve the polymer containing the imidazole side group. In general, the alcohol solvent may be selected from lower alcohols of C1 to C4, and examples thereof include methanol and ethanol.
In the step 1), in the alcohol solution of the polymer containing the imidazole side group, the concentration of the polymer containing the imidazole side group can be 0.01-0.1 g/mL. In addition, the imidazole side group-containing polymer is as described in the first aspect of the present invention and will not be described herein.
The nickel precursor is not particularly limited in the present invention and can be selected with reference to the prior art. Typically, the nickel precursor may be selected from nickel nitrate or nickel chloride, preferably nickel nitrate. In the alcohol solution of the nickel precursor, the concentration of the nickel precursor can be 0.01-0.1 g/mL.
In the present invention, the separation method of step 2) is well known in the art, and generally comprises processes of filtering, washing (for example, washing with toluene), drying, and the like. The drying is usually carried out under a vacuum condition, the drying temperature can be 60-80 ℃, and the drying time can be 4-8 hours.
In the invention, in the step 3), the carbonization can be carried out in an inert atmosphere, such as nitrogen, and the carbonization temperature can be 300-800 ℃; the carbonization time may be 1 to 12 hours. Preferably, the carbonization temperature is 400-600 ℃, and the carbonization time is 3-6 hours, so that the chemical adsorption amount of the catalyst to hydrogen can be further increased.
In the present invention, in step 4), the nickel oxide bonded to the carrier carbon can be reduced to a simple nickel substance by the hydrotreating, thereby obtaining a reduced matrix. The temperature of the hydrotreating can be 400-500 ℃; the hydrotreating time may be 2 to 24 hours, preferably 4 to 12 hours.
In the present invention, in step 5), the reduced substrate may be immersed in the aqueous solution of the ruthenium precursor for 1 to 48 hours, and preferably, the reduced substrate is immersed in the aqueous solution of the ruthenium precursor for 12 to 36 hours. By the soaking, the ruthenium precursor is dispersed and adsorbed on the substrate, and the ruthenium provided by the ruthenium precursor is provided by the nickel simple substance3+Reducing the nickel elementary substance into Ru, and oxidizing the nickel elementary substance into nickel metal ions, so that the ruthenium (Ru) is loaded on the substrate.
The ruthenium precursor is also not particularly limited in the present invention and may be selected with reference to the prior art. For example, the soluble salt of ruthenium may be ruthenium nitrate or ruthenium chloride. The concentration of ruthenium in the aqueous solution of the ruthenium precursor may be (5X 10)-6)～(1×10-3)g/mL。
According to the invention, the concentration of the alcohol solution of the polymer containing the imidazole side group is 0.01-0.1 g/mL, the concentration of the alcohol solution of the nickel precursor is 0.01-0.1 g/mL, and the volume ratio of the usage amount of the alcohol solution of the polymer containing the imidazole side group to the usage amount of the alcohol solution of the nickel precursor is (0.2-20): 1; the dosage of the ruthenium precursor is such that the weight ratio of the matrix to the ruthenium content in the obtained supported catalyst is 100: 0.01-1.0.
According to one embodiment of the invention, the supported catalyst is prepared by the following process: dripping the methanol solution of the nickel nitrate into the methanol solution of the polyvinyl imidazole under stirring, and keeping stirring for 0.5-12 hours; filtering the obtained reaction product, washing the reaction product with methanol for multiple times, drying the reaction product for 4 to 8 hours at 60 to 80 ℃ in vacuum, roasting the obtained solid powder for 1 to 12 hours (dehydrogenation weight loss) at 300 to 800 ℃ in a nitrogen atmosphere, treating the solid powder for 2 to 24 hours at 400 to 500 ℃ in hydrogen, soaking the solid subjected to hydrogenation treatment in an aqueous solution of a ruthenium precursor for 1 to 48 hours under the condition of air isolation, and performing adsorption and replacement (redox) reaction in the soaking process; filtering, washing with deionized water to be nearly neutral to obtain a supported catalyst, and placing in deionized water for storage.
According to a third aspect of the present invention, there is provided a supported catalyst obtained by the production method. The preparation method can prepare the supported catalyst. The supported catalyst of the invention combines nitrogen in the ruthenium carrier carbon with nickel by coordination bonds, so that the nickel is dispersed more uniformly, and the supported catalyst has higher hydrogen chemical adsorption amount by combining ruthenium, therefore, the supported catalyst has higher catalytic activity in the reaction with hydrogen.
To this end, according to a fourth aspect of the invention, there is provided the use of a supported catalyst of the invention in a hydrogenation reaction. The hydrogenation reaction includes, for example, a hydrogenation reaction of an unsaturated olefin such as an olefin and an alkyne, and a carbonyl hydrogenation reaction. The hydrogenation reaction takes hydrogen as a main reactant, and the supported catalyst can realize effective adsorption of the hydrogen and has high catalytic activity.
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.
Example 1
10mL of a 0.1g/mL methanol solution of polyvinylimidazole (Xn 2000) and 50mL of a 0.01g/mL methanol solution of nickel nitrate are taken; dripping a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole under the stirring state of the rotating speed of 300rpm, and then keeping stirring for 4 hours to generate a precipitate; filtering the stirred product, washing the obtained solid with methanol for 3 times, and then carrying out vacuum drying at 80 ℃ for 4 hours to obtain solid powder; and then roasting the solid powder for 4 hours at 300 ℃ in a nitrogen atmosphere to obtain the N-Ni/C-1 matrix with the nickel loading of 10 wt%.
Taking 50g of N-Ni/C-1 matrix, reducing the N-Ni/C-1 matrix for 8 hours at 450 ℃, and placing the reduced matrix in 500mL of Ru under the condition of air isolation3+Aqueous solution (Ru)3+Is 1 × 10-5g/mL ruthenium nitrate aqueous solution) for 24 hours, loading Ru on a substrate through adsorption and displacement reaction, filtering, washing with deionized water to be nearly neutral to obtain a supported catalyst containing 0.01 wt% of Ru, placing the supported catalyst in the deionized water for storage, and marking the catalyst as CAT-1.
Example 2
20mL of a methanol solution of polyvinyl imidazole (Xn: 2000) with a concentration of 0.05g/mL, and 10mL of a methanol solution of nickel nitrate with a concentration of 0.05 g/mL; dripping a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole under the stirring state of the rotating speed of 300rpm, and then keeping stirring for 4 hours to generate a precipitate; filtering the stirred product, washing the obtained solid with methanol for 3 times, and then carrying out vacuum drying at 80 ℃ for 4 hours to obtain solid powder; and then roasting the solid powder for 4 hours at 400 ℃ in a nitrogen atmosphere to obtain an N-Ni/C-2 matrix with the nickel loading of 54 wt%.
Taking 50g of N-Ni/C-2 matrix, reducing the N-Ni/C-2 matrix for 8 hours at 450 ℃, and placing the reduced matrix in 500mL of Ru under the condition of air isolation3+Aqueous solution (Ru)3+Is 1 × 10-4g/mL ruthenium nitrate aqueous solution) for 24 hours, by adsorption and attachmentAnd (3) carrying out a shift reaction, namely loading Ru on a substrate, filtering, washing with deionized water to be nearly neutral to obtain a supported catalyst containing 0.1 wt% of Ru, placing the supported catalyst in the deionized water for storage, and marking the catalyst as CAT-2.
Example 3
20mL of a methanol solution of polyvinyl imidazole (Xn: 2000) with a concentration of 0.05g/mL, and 10mL of a methanol solution of nickel nitrate with a concentration of 0.05 g/mL; under the state of stirring at the rotating speed of 300rpm, dripping a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole, and keeping stirring for 3 hours to generate a precipitate; filtering the stirred product, washing the obtained solid with methanol for 3 times, and vacuum-drying at 80 ℃ for 4 hours to obtain solid powder; and then the solid powder is roasted for 3 hours at 600 ℃ in the nitrogen atmosphere to obtain the N-Ni/C-3 matrix with the nickel loading of 58 wt%.
Taking 50g of N-Ni/C-3 matrix, reducing the N-Ni/C-3 matrix for 4 hours at 500 ℃, and placing the N-Ni/C-3 matrix in 500mL of Ru under the condition of air isolation3+Aqueous solution (Ru)3+Is 3 x 10-4g/mL ruthenium nitrate aqueous solution) for 30 hours, loading Ru on a substrate through adsorption and displacement reaction, filtering, washing with deionized water to be nearly neutral to obtain a supported catalyst containing 0.3 wt% of Ru, and placing the supported catalyst in the deionized water for storage, wherein the catalyst is marked as CAT-3.
Example 4
20mL of a methanol solution of polyvinyl imidazole (Xn: 2000) with a concentration of 0.05g/mL, and 10mL of a methanol solution of nickel nitrate with a concentration of 0.05 g/mL; under the state of stirring at the rotating speed of 300rpm, dripping a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole, and keeping stirring for 7 hours to generate a precipitate; filtering the stirred product, washing the product for 3 times by using methanol, and performing vacuum drying for 5 hours at the temperature of 80 ℃ to obtain solid powder; and then the solid powder is roasted for 5 hours at 600 ℃ in the nitrogen atmosphere to obtain the N-Ni/C-4 matrix with the nickel loading of 60 wt%.
Taking 50g of N-Ni/C-4 matrix, treating the matrix with hydrogen at 400 ℃ for 12 hours, and placing the matrix in 500mL of Ru under the condition of air isolation3+Aqueous solution (Ru)3+Is 8 x 10-4g/mL of ruthenium nitrate aqueous solution) for 32 hours, by adsorption and attachmentAnd (3) carrying out a shift reaction, namely loading Ru on a substrate, filtering, washing with deionized water to be nearly neutral to obtain a supported catalyst containing 0.8 wt% of Ru, and placing the supported catalyst in the deionized water for storage, wherein the catalyst is marked as CAT-4.
Example 5
100mL of a methanol solution of polyvinyl imidazole (Xn: 2000) with a concentration of 0.01g/mL, and 5mL of a methanol solution of nickel nitrate with a concentration of 0.1 g/mL; dripping a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole under the stirring state of the rotating speed of 300rpm, and then keeping stirring for 4 hours to generate a precipitate; filtering the stirred product, washing the obtained solid with methanol for 3 times, and then carrying out vacuum drying at 80 ℃ for 4 hours to obtain solid powder; and then the solid powder is roasted for 4 hours at 400 ℃ in the nitrogen atmosphere to obtain the N-Ni/C-5 matrix with the nickel loading of 51 wt%.
Taking 50g of N-Ni/C-5 matrix, reducing the N-Ni/C-5 matrix for 8 hours at 450 ℃, and placing the reduced matrix in 500mL of Ru under the condition of air isolation3+Aqueous solution (Ru)3+Is 1 × 10-4g/mL ruthenium nitrate aqueous solution) for 24 hours, loading Ru on a substrate through adsorption and displacement reaction, filtering, washing with deionized water to be nearly neutral to obtain a supported catalyst containing 0.1 wt% of Ru, placing the supported catalyst in the deionized water for storage, and marking the catalyst as CAT-5.
Example 6
Taking 50g of N-Ni/C-5 matrix, reducing the N-Ni/C-5 matrix for 8 hours at 450 ℃, and placing the reduced matrix in 500mL of Ru under the condition of air isolation3+Aqueous solution (Ru)3+Is 1 × 10-3g/mL ruthenium nitrate aqueous solution), loading Ru on a substrate through adsorption and displacement reaction, filtering, washing with deionized water to be nearly neutral to obtain a supported catalyst containing 1 wt% of Ru, placing the supported catalyst in the deionized water for storage, and marking the catalyst as CAT-6.
Comparative example 1
Ru/Al with an industrial Ru loading of 0.3 wt.% was used2O3The catalyst was a comparative catalyst.
The traditional load type Ru/Al is prepared by adopting an equivalent impregnation method2O3. In particular toTaking 10mL of Ru3+Adding ruthenium nitrate water solution with concentration of 0.003g/mL into 10g of macroporous alumina carrier (carrier water absorption rate is 105%), equivalently impregnating, filtering, drying the obtained solid at 110 ℃ for 12 hours, and roasting at 450 ℃ in air for 4 hours to obtain Ru/Al containing 0.3 wt% of Ru2O3A catalyst.
Ru/Al to be prepared2O3The catalyst was identified as CAT-D1 as a comparative catalyst after 8 hours of reductive treatment with hydrogen at 450 ℃.
Test example
Hydrogen chemisorption characterization
The performance of the catalysts of the above examples and comparative examples was evaluated and tested by chemisorption test H2The amount of chemisorption. Wherein H2The chemical adsorption amount is used as the judgment basis of the activity, and the specific characterization results are shown in Table 1 (the American Mike instruments ASPS2920 chemical adsorption instrument is adopted to test H under the conditions of normal pressure and 35 DEG C2Amount of chemisorption).
TABLE 1 hydrogen chemisorption amount of the catalyst
| Example numbering | Catalyst and process for preparing same | H2 chemisorption amount |
| Example 1 | CAT1 | 0.4mL/g cat. |
| Example 2 | CAT2 | 1.0mL/g cat. |
| Example 3 | CAT3 | 1.4mL/g cat. |
| Example 4 | CAT4 | 2.2mL/g cat. |
| Example 5 | CAT5 | 0.9mL/g cat. |
| Example 6 | CAT6 | 2.6mL/g cat. |
| Comparative example 1 | CAT-D1 | 0.3mL/g cat. |
The results in table 1 show that the supported catalyst of the present invention has a high hydrogen chemisorption amount and an activity significantly higher than that of the catalyst prepared by the conventional method.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (13)
1. A supported catalyst comprising a substrate and ruthenium supported thereon, wherein the substrate comprises nitrogen-doped support carbon and nickel, and at least a portion of the nickel forms coordination bonds with lone-pair electrons on the nitrogen.
2. The supported catalyst of claim 1, wherein the matrix is formed by carbonizing a polymeric support, which is a complex of a polymer containing pendant imidazole groups and a nickel precursor.
3. The supported catalyst according to claim 1 or 2, wherein the supported catalyst has a weight ratio of the matrix to the ruthenium content of 100: (0.01-1.0); the nickel content in the matrix is 10-60 wt%.
4. The supported catalyst of claim 2, wherein the polymer comprising pendant imidazole groups is selected from polyvinylimidazole or a vinylimidazole-divinylbenzene copolymer.
5. A method for preparing a supported catalyst, the method comprising:
1) dropwise adding the alcohol solution of the nickel precursor into the alcohol solution of the polymer containing the imidazole side group to perform a coordination reaction to obtain a reaction product of the polymer containing the imidazole side group and a complex of the nickel precursor;
2) separating the reaction product to obtain the complex serving as a high-molecular carrier;
3) carbonizing the polymer carrier to produce nitrogen-doped carrier carbon combined with nickel oxide;
4) carrying out hydrotreating on the carrier carbon in the step 3) to obtain a reduced matrix;
5) and (3) contacting the aqueous solution of the ruthenium precursor with the reduced substrate, and loading ruthenium on the substrate through adsorption and displacement reaction to obtain the supported catalyst.
6. The preparation method of claim 5, wherein the concentration of the alcohol solution of the polymer containing the imidazole side groups is 0.01-0.1 g/mL, the concentration of the alcohol solution of the nickel precursor is 0.01-0.1 g/mL, and the volume ratio of the usage amount of the alcohol solution of the polymer containing the imidazole side groups to the usage amount of the alcohol solution of the nickel precursor is (0.2-20): 1; the dosage of the ruthenium precursor is such that the weight ratio of the matrix to the ruthenium content in the obtained supported catalyst is 100: 0.01-1.0.
7. The method of claim 5 or 6, wherein the polymer containing pendant imidazole groups is selected from polyvinylimidazole or a vinylimidazole-divinylbenzene copolymer.
8. The production method according to any one of claims 5 to 7, wherein, in step 1), the coordination reaction is performed under stirring conditions including: the stirring speed is 50-600 rpm, preferably 200-400 rpm; the stirring time is 0.5 to 12 hours, preferably 3 to 8 hours.
9. The production method according to any one of claims 5 to 8, wherein in step 3), the carbonization conditions include: the temperature is 300-800 ℃, preferably 400-600 ℃; the time is 1 to 12 hours, preferably 3 to 6 hours.
10. The production method according to any one of claims 5 to 9, wherein in step 4), the conditions of the hydrotreatment include: the temperature is 400-500 ℃, and the time is 2-24 hours, preferably 4-12 hours.
11. The production method according to any one of claims 5 to 10, wherein step 5) includes: and soaking the reduced substrate for 1-48 hours by using an aqueous solution of a ruthenium precursor, preferably for 12-36 hours.
12. A supported catalyst obtained by the production method according to any one of claims 5 to 11.
13. Use of a supported catalyst according to any one of claims 1 to 4 and 12 in a hydrogenation reaction.
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| CN103934027A (en) * | 2014-04-24 | 2014-07-23 | 南京德灿化学有限公司 | Solid acid catalyst as well as preparation method and application thereof |
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