CN114471651B - Supported catalyst and preparation method and application thereof - Google Patents
Supported catalyst and preparation method and application thereof Download PDFInfo
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- CN114471651B CN114471651B CN202011158799.9A CN202011158799A CN114471651B CN 114471651 B CN114471651 B CN 114471651B CN 202011158799 A CN202011158799 A CN 202011158799A CN 114471651 B CN114471651 B CN 114471651B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 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 115
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 52
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 42
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 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
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 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 66
- 239000011159 matrix material Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 38
- 239000002243 precursor Substances 0.000 claims description 35
- 229920000642 polymer Polymers 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000006073 displacement reaction Methods 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000002883 imidazolyl group Chemical group 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 5
- 238000010000 carbonizing Methods 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 87
- 239000007787 solid Substances 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000001914 filtration Methods 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 13
- 238000011068 loading method Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 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
- 230000007935 neutral effect Effects 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000126 substance Substances 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 4
- 230000000694 effects Effects 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
- 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
- 239000003999 initiator Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 nickel salt Chemical class 0.000 description 2
- 238000012360 testing method Methods 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
- 229910018072 Al 2 O 3 Inorganic materials 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
- 230000001476 alcoholic effect Effects 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
- 125000004432 carbon atom Chemical group C* 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
- 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
- 239000006185 dispersion Substances 0.000 description 1
- 239000012467 final product Substances 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
- 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
- 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
- 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
- 238000001291 vacuum drying Methods 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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- 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, a preparation method and application thereof. The supported catalyst comprises a substrate and ruthenium supported thereon, wherein the substrate comprises nitrogen-doped carrier carbon and nickel, and a coordination bond is formed between at least part of the nickel and 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
A noble metal catalyst is a noble metal material that can alter the rate of a chemical reaction without itself participating in the final product of the reaction. 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, researches on supported Ru catalysts are mainly focused on catalyst preparation and application, and catalysts required by reactions such as hydrogenation or dehydrogenation are usually obtained by using different carriers, different Ru precursors, different preparation methods and the like. For example, alumina-supported Ru catalysts are obtained by impregnation methods using alumina supports; the method comprises the steps of (1) obtaining a coconut shell carbon supported 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 can be used for 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, there is a need to develop a high-activity Ru catalyst capable of improving the utilization of noble metal Ru.
Disclosure of Invention
The invention aims to provide a supported catalyst, a preparation method and application thereof, wherein the catalyst has high catalytic activity and a simple preparation method.
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 wherein a coordination bond is formed between at least a portion of the nickel and a lone pair of electrons on the nitrogen.
In a second aspect, the present invention provides a method for preparing a supported catalyst, the method comprising:
1) Adding an alcohol solution of a nickel precursor into an alcohol solution of a polymer containing imidazole side groups in a dropwise manner to carry out a coordination reaction, so as to obtain a reaction product of a complex of the polymer containing imidazole side groups and the nickel precursor;
2) Separating the reaction product to obtain the complex serving as a high molecular carrier;
3) Carbonizing the polymer carrier to generate nitrogen-doped carrier carbon combined with nickel oxide;
4) Hydrotreating the carrier carbon of the step 3) to obtain a reduced matrix;
5) And (3) enabling the aqueous solution of the ruthenium precursor to contact with the reduced matrix, and carrying out adsorption and displacement reaction to enable ruthenium to be loaded on the matrix, so as to obtain the supported catalyst.
In a third aspect, the present invention provides a supported catalyst obtainable by the process according to the second aspect of the invention.
In a fourth aspect, the present invention provides the use of the supported catalyst in hydrogenation reactions.
The supported catalyst provided by the invention is a supported Ru catalyst, and does not contain a traditional oxide or active carbon carrier, the catalyst uses nitrogen-doped carrier carbon obtained by high-molecular carbonization and combines nickel as a matrix, coordination bonds exist between nitrogen and metal nickel in the matrix, so that the dispersion of the metal nickel is more uniform, the valence electronic structure is changed due to the coordination bonds, and the catalyst has the advantages of high catalytic activity, good selectivity, stability and the like by combining ruthenium. In addition, in the preparation method provided by the invention, the whole process can be carried out under the anaerobic condition, and the operation of high-temperature roasting of the ruthenium-containing precursor in the oxygen-containing atmosphere in the traditional preparation process of the ruthenium catalyst can be avoided, so that the emission problem 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 specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
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 a coordination bond is formed between at least a portion of the nickel (Ni) and the lone pair electrons on nitrogen (N). Specifically, the matrix comprises an in-situ generated nitrogen-containing carbon carrier and nickel coordinately supported on the carbon carrier.
In the present invention, the matrix may be formed by carbonization of a polymer carrier. Wherein the high molecular carrier is a complex of a polymer containing imidazole side groups and a nickel precursor (nickel salt). In the polymer carrier, coordination bonds are formed between nickel and lone pair electrons on nitrogen atoms in imidazole side groups, after high-temperature carbonization, polymers are dehydrogenated and weightlessly formed into carbon, nitrogen elements on imidazole groups of the polymers are partially reserved due to coordination with nickel, then nitrogen-doped carbon materials are formed, nickel salts are decomposed by utilizing carbonized high temperature, and 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 through coordination bonds, so that the nickel is dispersed more uniformly.
In the present invention, in the polymer containing imidazole side groups, the molecular chain of the polymer contains a repeating structural unit, and each repeating unit may contain an imidazole group to form a side chain of the whole molecule. The polymer containing imidazole side groups is not particularly limited in the present invention, as long as the carbon support can be formed by carbonization. Preferably, the polymer containing imidazole side 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 may be prepared by methods well known in the art (e.g., by free radical polymerization using AIBN as an initiator) or may be obtained commercially. In general, the degree of polymerization (Xn) of the polyvinylimidazole may be 1000 to 10000. For example, polyvinyl imidazole with Xn of 2000 is obtained by reaction in a hydrothermal kettle at 60 ℃ using AIBN as initiator and toluene as solvent.
In the present invention, the weight ratio of the base to the ruthenium content in the supported catalyst is 100: (0.01-1.0), preferably 100: (0.1-1.0); the nickel content of the matrix is 10 to 60wt%, preferably 45 to 60 wt%. The ruthenium content was calculated from the feed amount and the nickel content was measured by X-ray fluorescence spectroscopy (XRF) analysis.
According to a second aspect of the present invention, there is provided a method of preparing a supported catalyst, the method comprising:
1) Adding an alcohol solution of a nickel precursor into an alcohol solution of a polymer containing imidazole side groups in a dropwise manner to carry out a coordination reaction, so as to obtain a reaction product of a complex of the polymer containing imidazole side groups and the nickel precursor;
2) Separating the reaction product to obtain the complex serving as a high molecular carrier;
3) Carbonizing the polymer carrier to generate nitrogen-doped carrier carbon combined with nickel oxide;
4) Hydrotreating the carrier carbon of the step 3) to obtain a reduced matrix;
5) And (3) enabling the aqueous solution of the ruthenium precursor to contact with the reduced matrix, and carrying out adsorption and displacement reaction to enable ruthenium to be loaded on the matrix, so as 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 groups in the polymer to form a complex of the polymer containing imidazole side groups and the nickel precursor. The coordination reaction is carried out 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.
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 dissolve the polymer containing imidazole side groups. In general, the alcohol solvent may be selected from lower alcohols having 1 to 4 carbon atoms, and may be methanol, ethanol, or the like.
In step 1), the concentration of the polymer containing imidazole side groups in the alcoholic solution of the polymer containing imidazole side groups may be 0.01 to 0.1g/mL. In addition, the polymer containing imidazole side groups is described in the first aspect of the present invention, and is not described herein.
The nickel precursor is not particularly limited and may 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 includes filtration, washing (e.g., washing with toluene), drying, and the like. The drying is usually carried out under vacuum conditions, the drying temperature may be 60 to 80 ℃, and the drying time may be 4 to 8 hours.
In the present invention, in step 3), the carbonization may be performed under an inert atmosphere, for example, under nitrogen, and the carbonization temperature may be 300 to 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 chemisorption amount of the catalyst to the hydrogen can be further improved.
In the present invention, in step 4), the nickel oxide bound to the support carbon may be reduced to a simple nickel substance by the hydrotreatment, thereby obtaining a reduced substrate. The temperature of the hydrotreatment 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, preferably the reduced substrate is immersed in the aqueous solution of the ruthenium precursor for 12 to 36 hours. Through the soaking, the ruthenium precursor is dispersed and adsorbed on the matrix, and the Ru provided by the ruthenium precursor is obtained by utilizing the simple substance of nickel 3+ Reduced to Ru while the elemental nickel is oxidized to nickel metal ions, so that ruthenium (Ru) is supported on the substrate.
The ruthenium precursor is also not particularly limited in the present invention, and can 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 (5×10) -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 alcohol solution of the polymer containing the imidazole side group to the use amount of the alcohol solution of the nickel precursor is (0.2-20) to 1; the ruthenium precursor is used in such an amount that the weight ratio of the base to the ruthenium content in the resulting supported catalyst is 100:0.01-1.0.
According to one embodiment of the invention, the supported catalyst is prepared by the following process: dropwise adding a methanol solution of nickel nitrate into a methanol solution of 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 in vacuum at 60-80 ℃ for 4-8 hours, roasting the obtained solid powder at 300-800 ℃ for 1-12 hours (dehydrogenation weightlessness) in nitrogen atmosphere, then treating the solid powder at 400-500 ℃ for 2-24 hours in hydrogen, and then soaking the hydrotreated solid in an aqueous solution of ruthenium precursor for 1-48 hours under the condition of isolating air, wherein the solid powder undergoes adsorption and displacement (redox) reactions in the soaking process; filtering, washing with deionized water to be close to neutral to obtain a supported catalyst, and storing in deionized water.
According to a third aspect of the present invention, there is provided a supported catalyst produced by the production method. The preparation method can prepare the supported catalyst. The supported catalyst of the invention combines nitrogen in ruthenium carrier carbon with nickel in coordination bond, so that nickel is dispersed more uniformly, and the supported catalyst has higher hydrogen chemisorption amount by combining ruthenium, thus having higher catalytic activity in the reaction with hydrogen.
To this end, according to a fourth aspect of the invention, the present invention provides the use of the supported catalyst of the invention in hydrogenation reactions. The hydrogenation reaction includes, for example, hydrogenation reaction of unsaturated olefins such as olefins and alkynes, and hydrogenation reaction of carbonyl groups. 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 examples, but the scope of the present invention is not limited to these examples.
Example 1
Taking 10mL of methanol solution with the concentration of 0.1g/mL of polyvinyl imidazole (Xn=2000), and taking 50mL of methanol solution with the concentration of 0.01g/mL of nickel nitrate; dripping a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole under the stirring condition of 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 drying the solid in vacuum at 80 ℃ for 4 hours to obtain solid powder; and roasting the solid powder in a nitrogen atmosphere at 300 ℃ for 4 hours to obtain the N-Ni/C-1 matrix with the nickel loading of 10 weight percent.
Taking 50g of N-Ni/C-1 matrix, reducing with hydrogen at 450 ℃ for 8 hours, placing the reduced matrix in 500mL Ru under the condition of isolating air 3+ Aqueous solution (Ru) 3+ Is 1X 10 -5 g/mL ruthenium nitrate aqueous solution), loading Ru on a substrate by adsorption and displacement reaction, filtering, washing with deionized water to be nearly neutral to obtain a supported catalyst containing 0.01wt% Ru, placing in deionized water for preservation, and recording the catalyst as CAT-1.
Example 2
Taking 20mL of methanol solution with the concentration of 0.05g/mL of polyvinyl imidazole (Xn=2000), and taking 10mL of methanol solution with the concentration of 0.05g/mL of nickel nitrate; dripping a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole under the stirring condition of 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 drying the solid in vacuum at 80 ℃ for 4 hours to obtain solid powder; and roasting the solid powder in a nitrogen atmosphere at 400 ℃ for 4 hours to obtain the N-Ni/C-2 matrix with the nickel loading of 54 weight percent.
Taking 50g of N-Ni/C-2 matrix, reducing with hydrogen at 450 ℃ for 8 hours, placing the reduced matrix in 500mL Ru under the condition of isolating air 3+ Aqueous solution (Ru) 3+ Is 1X 10 -4 g/mL ruthenium nitrate aqueous solution), loading Ru on a substrate by adsorption and displacement reaction, filtering, washing to be nearly neutral by using deionized water to obtain a supported catalyst containing 0.1wt% Ru, placing the supported catalyst in deionized water for preservation, and marking the catalyst as CAT-2.
Example 3
Taking 20mL of methanol solution with the concentration of 0.05g/mL of polyvinyl imidazole (Xn=2000), and taking 10mL of methanol solution with the concentration of 0.05g/mL of nickel nitrate; dripping the methanol solution of nickel nitrate into the methanol solution of polyvinyl imidazole under the stirring state of rotating speed 300rpm, and keeping stirring for 3 hours to generate 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 roasting the solid powder in a nitrogen atmosphere at 600 ℃ for 3 hours to obtain the N-Ni/C-3 matrix with 58 weight percent of nickel loading.
50g of N-Ni/C-3 matrix is taken and reduced with hydrogen at 500 ℃ for 4 hours, and is placed in 500mL Ru under the condition of air isolation 3+ Aqueous solution (Ru) 3+ Is 3X 10 -4 g/mL ruthenium nitrate aqueous solution) for 30 hours, loading Ru on a matrix through adsorption and displacement reaction, filtering, washing to be nearly neutral by using deionized water to obtain a supported catalyst containing 0.3wt% Ru, and placing the supported catalyst in the deionized water for preservation, wherein the catalyst is named CAT-3.
Example 4
Taking 20mL of methanol solution with the concentration of 0.05g/mL of polyvinyl imidazole (Xn=2000), and taking 10mL of methanol solution with the concentration of 0.05g/mL of nickel nitrate; dripping the methanol solution of nickel nitrate into the methanol solution of polyvinyl imidazole under the stirring state of rotating speed 300rpm, and keeping stirring for 7 hours to generate precipitate; filtering the stirred product, washing the product with methanol for 3 times, and drying the product in vacuum at 80 ℃ for 5 hours to obtain solid powder; and roasting the solid powder in a nitrogen atmosphere at 600 ℃ for 5 hours to obtain the N-Ni/C-4 matrix with the nickel loading of 60 wt%.
50g of N-Ni/C-4 matrix is taken, treated with hydrogen at 400 ℃ for 12 hours, and placed in 500mL Ru under the condition of air isolation 3+ Aqueous solution (Ru) 3+ Is 8 multiplied by 10 -4 g/mL of ruthenium nitrate aqueous solution) for 32 hours, loading Ru on a matrix through adsorption and displacement reaction, filtering, washing to be nearly neutral by using deionized water to obtain a supported catalyst containing 0.8wt% Ru, and placing the supported catalyst in the deionized water for preservation, wherein the catalyst is named CAT-4.
Example 5
Taking 100mL of methanol solution with the concentration of 0.01g/mL of polyvinyl imidazole (Xn=2000), and taking 5mL of methanol solution with the concentration of 0.1g/mL of nickel nitrate; dripping a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole under the stirring condition of 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 drying the solid in vacuum at 80 ℃ for 4 hours to obtain solid powder; and roasting the solid powder in a nitrogen atmosphere at 400 ℃ for 4 hours to obtain the N-Ni/C-5 matrix with the nickel loading amount of 51 wt%.
Taking 50g of N-Ni/C-5 matrix, reducing with hydrogen at 450 ℃ for 8 hours, placing the reduced matrix in 500mL Ru under the condition of isolating air 3+ Aqueous solution (Ru) 3+ Is 1X 10 -4 g/mL ruthenium nitrate aqueous solution), loading Ru on a substrate by adsorption and displacement reaction, filtering, washing with deionized water to be nearly neutral to obtain a supported catalyst containing 0.1wt% Ru, placing in deionized water for preservation, and recording the catalyst as CAT-5.
Example 6
Taking 50g of N-Ni/C-5 matrix, reducing with hydrogen at 450 ℃ for 8 hours, placing the reduced matrix in 500mL Ru under the condition of isolating air 3+ Aqueous solution (Ru) 3+ Is 1X 10 -3 g/mL ruthenium nitrate aqueous solution), loading Ru on a matrix through adsorption and displacement reaction, filtering, washing to be nearly neutral by using deionized water to obtain a supported catalyst containing 1wt% Ru, placing the supported catalyst in the deionized water for preservation, and marking the catalyst as CAT-6.
Comparative example 1
Ru/Al with commercial Ru loadings of 0.3wt% 2 O 3 The catalyst is a comparative catalyst.
The equivalent impregnation method is adopted to prepare the traditional load Ru/Al 2 O 3 . Specifically, 10mL Ru was taken 3+ Ruthenium nitrate aqueous solution with concentration of 0.003g/mL is added with 10g macroporous alumina carrier (carrier water absorption rate is 105%), after equal impregnation, the obtained solid is filtered, dried for 12 hours at 110 ℃, and baked for 4 hours at 450 ℃ in air, thus obtaining Ru/Al containing 0.3wt% Ru 2 O 3 A catalyst.
Ru/Al to be prepared 2 O 3 The catalyst was reduced with hydrogen at 450℃for 8 hours and was designated CAT-room temperature catalyst as a comparative catalystD1。
Test case
Hydrogen chemisorption characterization
The catalyst performance of the above examples and comparative examples was evaluated and tested for H by chemisorption 2 Chemisorption amount. Wherein H is 2 The chemical adsorption amount is used as the judging basis of the activity, and the specific characterization result is shown in Table 1 (the test H is carried out by adopting an ASPS2920 chemical adsorption instrument of America microphone company under the conditions of normal pressure and 35℃) 2 Chemisorption amount).
Table 1 chemisorption amount of hydrogen on catalyst
Examples numbering | Catalyst | Amount of chemisorption of H2 |
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. |
As can be seen from the results of table 1, the supported catalyst of the present invention has a higher hydrogen chemisorption amount and a significantly higher activity than the catalyst prepared by the conventional method.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or 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 various embodiments described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (16)
1. A supported catalyst comprising a substrate and ruthenium supported thereon, wherein the substrate comprises nitrogen-doped support carbon and nickel, and wherein a coordination bond is formed between at least a portion of the nickel and a lone pair of electrons on the nitrogen;
the matrix is formed by carbonizing a high polymer carrier, and the high polymer carrier is a complex of a polymer containing imidazole side groups and a nickel precursor.
2. The supported catalyst according to claim 1, wherein the weight ratio of the matrix to ruthenium content in the supported catalyst is 100: (0.01-1.0); the nickel content of the matrix is 10 to 60 wt%.
3. The supported catalyst of claim 1, wherein the polymer containing imidazole side groups is selected from a polyvinylimidazole or a vinylimidazole-divinylbenzene copolymer.
4. A method for preparing a supported catalyst, comprising:
1) Adding an alcohol solution of a nickel precursor into an alcohol solution of a polymer containing imidazole side groups in a dropwise manner to carry out a coordination reaction, so as to obtain a reaction product of a complex of the polymer containing imidazole side groups and the nickel precursor;
2) Separating the reaction product to obtain the complex serving as a high molecular carrier;
3) Carbonizing the polymer carrier to generate nitrogen-doped carrier carbon combined with nickel oxide;
4) Hydrotreating the carrier carbon of the step 3) to obtain a reduced matrix;
5) And (3) enabling the aqueous solution of the ruthenium precursor to contact with the reduced matrix, and carrying out adsorption and displacement reaction to enable ruthenium to be loaded on the matrix, so as to obtain the supported catalyst.
5. The preparation method according to claim 4, wherein the concentration of the alcohol solution of the polymer containing 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 alcohol solution of the polymer containing imidazole side groups to the amount of the alcohol solution of the nickel precursor is (0.2-20) to 1; the ruthenium precursor is used in such an amount that the weight ratio of the base to the ruthenium content in the resulting supported catalyst is 100:0.01-1.0.
6. The process of claim 4, wherein the polymer containing pendant imidazole groups is selected from the group consisting of polyvinylimidazole or vinylimidazole-divinylbenzene copolymers.
7. The production method according to any one of claims 4 to 6, wherein in step 1), the coordination reaction is performed under stirring conditions including: the stirring speed is 50-600 rpm; the stirring time is 0.5-12 hours.
8. The process according to claim 7, wherein in step 1), the stirring speed is 200 to 400rpm and the stirring time is 3 to 8 hours.
9. The production method according to any one of claims 4 to 6, wherein in step 3), the carbonization conditions include: the temperature is 300-800 ℃; the time is 1-12 hours.
10. The production method according to claim 9, wherein in step 3), the carbonization conditions include: the temperature is 400-600 ℃ and the time is 3-6 hours.
11. The production method according to any one of claims 4 to 6, wherein in step 4), the hydrotreating conditions include: the temperature is 400-500 ℃ and the time is 2-24 hours.
12. The production process according to claim 11, wherein in step 4), the hydrotreating time is 4 to 12 hours.
13. The production method according to any one of claims 4 to 6, wherein step 5) comprises: soaking the reduced matrix for 1-48 hours by using an aqueous solution of ruthenium precursor.
14. The method of manufacturing according to claim 13, wherein step 5) comprises: soaking the reduced matrix for 12-36 hours by using an aqueous solution of ruthenium precursor.
15. A supported catalyst produced by the production process according to any one of claims 4 to 14.
16. Use of a supported catalyst according to any one of claims 1-3 and 15 in a hydrogenation reaction.
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5141911A (en) * | 1989-08-10 | 1992-08-25 | Societe Nationale Elf Aquitaine | Oxidation catalysts based on supported metalloporphyrin |
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CN111293300A (en) * | 2020-02-28 | 2020-06-16 | 中南大学 | Zinc-cobalt sulfide/carbon nano anode material and preparation method thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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US5141911A (en) * | 1989-08-10 | 1992-08-25 | Societe Nationale Elf Aquitaine | Oxidation catalysts based on supported metalloporphyrin |
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 |
CN111054438A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | Composite catalyst and preparation method and application thereof |
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