CN115282959B - Ru-Nb-Ce trimetallic catalyst loaded by carbon nano tube, method and application thereof in preparing coconut aldehyde - Google Patents
Ru-Nb-Ce trimetallic catalyst loaded by carbon nano tube, method and application thereof in preparing coconut aldehyde Download PDFInfo
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- CN115282959B CN115282959B CN202210895173.9A CN202210895173A CN115282959B CN 115282959 B CN115282959 B CN 115282959B CN 202210895173 A CN202210895173 A CN 202210895173A CN 115282959 B CN115282959 B CN 115282959B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 34
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 34
- OALYTRUKMRCXNH-UHFFFAOYSA-N 5-pentyloxolan-2-one Chemical compound CCCCCC1CCC(=O)O1 OALYTRUKMRCXNH-UHFFFAOYSA-N 0.000 title abstract description 17
- 238000000034 method Methods 0.000 title abstract description 13
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 86
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 150000002739 metals Chemical class 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 24
- 239000012018 catalyst precursor Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 238000006722 reduction reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 2
- CGAFRZVAXRQUEI-UHFFFAOYSA-N niobium(5+);propan-1-olate Chemical compound [Nb+5].CCC[O-].CCC[O-].CCC[O-].CCC[O-].CCC[O-] CGAFRZVAXRQUEI-UHFFFAOYSA-N 0.000 claims description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 244000060011 Cocos nucifera Species 0.000 abstract description 16
- 235000013162 Cocos nucifera Nutrition 0.000 abstract description 16
- 239000003999 initiator Substances 0.000 abstract description 4
- 150000003254 radicals Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000000066 reactive distillation Methods 0.000 description 7
- 235000002639 sodium chloride Nutrition 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000019634 flavors Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 244000144725 Amygdalus communis Species 0.000 description 2
- 235000011437 Amygdalus communis Nutrition 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000020224 almond Nutrition 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000686 essence Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- -1 aryl piperidine Chemical compound 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000457 gamma-lactone group Chemical group 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
-
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
Abstract
The invention discloses a Ru-Nb-Ce trimetallic catalyst loaded by carbon nano tubes, a method and application thereof in preparing coconut aldehyde, wherein the catalyst comprises metals Ru, nb and Ce serving as active components and carbon nano tubes serving as carriers; the mol ratio of the Ru, the Nb and the Ce of the metal is 1 (0.1-0.5) to 0.1-0.8; in the catalyst, the mass of the carbon nano tube is 45-55 times of the total mass of metals Ru, nb and Ce. The catalyst can catalyze the reaction of n-hexanol and methyl acrylate under the condition of no free radical initiator, and can prepare cocoanut aldehyde with high activity and high yield.
Description
Technical Field
The invention relates to a catalyst, in particular to a Ru-Nb-Ce trimetallic catalyst loaded by carbon nano tubes, a method and application thereof in preparing coconut aldehyde.
Background
Coconut aldehyde is a unique name of gamma-nonolactone, is a light yellow or colorless oily liquid, has coconut flavor when concentrated, has almond flavor or peach blossom flavor when diluted, and can be used in essence requiring oil and fat smell and a plurality of flavoring essences, such as coconut and almond essences. The chemical structural expression of the coco aldehyde is shown as formula I:
at present, a plurality of synthesis methods of coconut aldehyde exist at home and abroad:
document (Flavour and Fragrance Journal 2006,21 (3), 395-399.) reports a process for producing cocoaldehyde by cyclization of a beta, gamma-unsaturated acid in the presence of a catalyst such as polyphosphoric acid, an acidic ion exchange resin, and solid phosphoric acid, in a yield of 52.3%. The method has short synthetic route and simple reaction condition, but has more byproducts, low product yield and quality and no environmental economy due to the strong oxidizing property of the concentrated sulfuric acid.
Literature (Tetrahedron Lett,1980, 21:1735-1738.) reports that gamma-hydroxy carboxylic acid is obtained first from gamma-alkynol as starting material, and then intramolecular esterification under the action of acid gives gamma-lactone with a product yield of 64%. The route needs to use n-butyllithium, has harsh process conditions, and is difficult to obtain raw materials and apply to industrial production.
A large number of patent JP04275282A, JP04275283A, CN102617522a reports that n-hexanol and methyl acrylate can be prepared into cocoaldehyde in the presence of a free radical initiator, but the product yield is low, and methyl acrylate is extremely easy to polymerize in the presence of the free radical initiator to generate more byproducts, so that the components of the product are complex, the energy consumption of rectification and purification is increased, and the like.
In view of the above, it is necessary to develop a highly efficient catalyst useful for preparing cocoanut aldehyde, which is significant in improving reaction yield and selectivity and reducing energy consumption of the product.
Disclosure of Invention
In order to solve the technical problems, the invention provides a Ru-Nb-Ce trimetallic catalyst loaded by carbon nano tubes, a method and application thereof in preparing coconut aldehyde.
According to one aspect of the invention, a Ru-Nb-Ce trimetallic catalyst loaded by carbon nano tubes is provided, and can catalyze the reaction of n-hexanol and methyl acrylate under the condition of no free radical initiator, and coconut aldehyde is prepared with high activity and high yield.
Based on another aspect of the invention, a preparation method of the Ru-Nb-Ce trimetallic catalyst loaded by the carbon nano tube is also provided.
Based on another aspect of the invention, the invention also provides an application of the Ru-Nb-Ce trimetallic catalyst loaded by the carbon nano tube in preparing cocoanut aldehyde.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a carbon nanotube-supported Ru-Nb-Ce trimetallic catalyst for the preparation of coco aldehyde, the catalyst comprising metals Ru, nb, ce as active components, and carbon nanotubes as a support;
the molar ratio of the metals Ru, nb and Ce is 1 (0.1-0.5): (0.1-0.8), preferably 1 (0.2-0.3): (0.4-0.6), such as 1:0.1:0.1, 1:0.1:0.8, 1:0.5:0.1, 1:0.5:0.8, 1:0.2:0.4, 1:0.3:0.6, 1:0.2:0.5, 1:0.3:0.3, etc.
In the catalyst, the mass of the carbon nano tube is 45-55 times of the total mass of the metal Ru, nb and Ce, for example, 45 times, 47 times, 50 times, 52 times, 55 times and the like, calculated by metal ions.
The trimetallic catalyst provided by the invention takes the carbon nano tube as a carrier, has a rich mesoporous channel structure, and can increase the load capacity of the metal active center, thereby improving the utilization rate of the trimetallic catalyst. In addition, the metal Nb, ce and the metal Ru are taken as active centers together, so that the catalyst has important synergistic enhancement effect in the aspects of inhibiting the self-polymerization of methyl acrylate, improving the catalytic activity and the reaction selectivity, and is beneficial to greatly improving the reaction conversion rate and the selectivity.
In a preferred embodiment of the present invention, the catalyst is prepared by obtaining a solid from a mixture of a metal precursor and carbon nanotubes by a precipitation method, and then reducing the solid by hydrogen and roasting the solid.
The invention also provides a preparation method of the trimetallic catalyst, which comprises the following steps:
1) Placing metal precursors Ru salt, nb salt and Ce salt into deionized water, adding ammonia water to adjust the pH to 8-10, uniformly adding carbon nano tubes into the obtained solution after complete dissolution, and stirring and dispersing to obtain a mixture containing black precipitates;
the addition of ammonia water has two functions, namely, ammonia coordination of Ru, nb and Ce ions can be realized, and metal ions are prevented from being precipitated prematurely, so that the metal is unevenly dispersed; secondly, the electric neutrality of the surface of the pore canal of the carbon nano tube can be changed, and a foundation is laid for positively charged Ru, nb and Ce ions to realize high dispersion load through the action of charges.
2) Filtering the mixture obtained in the step 1) to obtain a catalyst precursor; and (3) placing the catalyst precursor in a hydrogen reducing atmosphere for reduction, filtering and drying, and roasting in an inert atmosphere to obtain the Ru-Nb-Ce trimetallic catalyst loaded by the carbon nano tube.
In a preferred embodiment of the present invention, the Ru salt is one or more of ruthenium trichloride, ruthenium acetate; the Nb salt is one or more of niobium pentachloride, niobium oxalate and niobium n-propoxide; the Ce salt is one or more of cerium trichloride, cerium nitrate and cerium acetate.
In a preferred embodiment of the present invention, in step 1), after adding the carbon nanotubes, the stirring and dispersing conditions are: the stirring temperature is 50-90 ℃, preferably 70-80 ℃, and the stirring time is 5-10h, preferably 7-8h.
In a preferred embodiment of the invention, in step 2), the reduction of the catalyst precursor is carried out in a hydrogen generator electrolyzer, and the catalyst precursor is reduced by hydrogen produced by electrolysis of water to increase the specific surface area and catalytic activity of the catalyst.
Preferably, the hydrogen flow rate generated by the hydrogen generator electrolyzer is 0.5-2L/min.
In a preferred embodiment of the present invention, the hydrogen generator electrolyzer comprises an electrolyte, a cathode electrode, an anode electrode, and a separator;
the electrolyte is one or more of aqueous solutions of sodium hydroxide, potassium hydroxide, sodium chloride, sodium sulfate and potassium chloride; the mass concentration of the electrolysis may be, for example, 10 to 40%, preferably 10%, 15%, 20%, 25%, 30%, 35%, 40%, etc.
The cathode electrode is made of any one or a combination of a plurality of platinum, rhodium, molybdenum carbide and cobalt phosphide;
the anode electrode is any one or a combination of a plurality of graphite, cobalt oxide, iridium oxide and perovskite;
the diaphragm is any one or a combination of a plurality of asbestos cloth, polysulfone anion exchange membrane, polyphenyl ether anion exchange membrane and polyether-free aryl piperidine;
preferably, the electrolysis conditions in the hydrogen generator electrolysis cell are: the current density is 0.1-0.4A/cm 2 The voltage interval is 1-3V.
In a preferred embodiment of the invention, in step 2), the calcination conditions are: the temperature is 350-500 ℃, preferably 400-450 ℃ for 5-10 hours, preferably 6-8 hours.
The invention also provides an application of the trimetallic catalyst or the trimetallic catalyst prepared by the method in preparing cocoaldehyde by catalyzing the reaction of n-hexanol and methyl acrylate.
In a preferred embodiment of the present invention, the methyl acrylate and the excess n-hexanol are reacted in the presence of a trimetallic catalyst to produce cocoaldehyde;
preferably, the reaction conditions are: the reaction temperature is 70-150 ℃, preferably 90-110 ℃, and the reaction time is 3-8h, preferably 4-6h;
preferably, the molar ratio of n-hexanol to methyl acrylate is 2-5:1, preferably 3-4:1;
preferably, the amount of the trimetallic catalyst added in the reaction is 0.5-1.5% by mass, preferably 0.8-1.2% by mass, of methyl acrylate.
The invention has the beneficial effects that:
the trimetallic catalyst composed of the active components of metal Ru, nb and Ce and the carbon nano tube carrier is used as a catalyst for preparing cocoaldehyde by the reaction of n-hexanol and methyl acrylate, and can effectively inhibit the polymerization of methyl acrylate, thereby reducing the generation of polymerization byproducts and improving the product yield and quality. In addition, the catalyst has higher reaction conversion rate and selectivity when being applied to the reaction of n-hexanol and methyl acrylate to prepare cocoaldehyde; and the catalyst is easy to recycle, the reaction condition is mild, and the method is suitable for industrial application production.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The materials and reagents used in the following embodiments were obtained by commercially available methods unless otherwise specified. Among them, carbon nanotubes were purchased from aladine (trade mark C124533).
Gas chromatography detection conditions:
GC-9800 chromatograph analysis, chromatographic conditions were: the initial temperature is 120 ℃, kept for 2min, and the temperature is programmed to be 280 ℃ at the speed of 20 ℃/min, and kept for 10min; the temperature of the gasification chamber is 300 ℃, and the temperature of the detection chamber is 300 ℃; FID detection; the sample loading was 0.2. Mu.l.
The following specific embodiments uniformly adopt the following conditions of the hydrogen generator electrolytic cell:
the electrolyte is 25% potassium hydroxide aqueous solution, the diaphragm is asbestos cloth, and the current density is 0.25A/cm 2 The voltage interval is 2V, the cathode material is platinum, and the anode material is graphite; the flow rate of the generated hydrogen was 1L/min.
[ example 1 ]
(1) Preparation of catalyst A
To 400g of deionized water was added 0.5g of ruthenium acetate, 0.107g of NbCl 5 、0.293g Ce(NO 3 ) 3 Dissolving and stirring uniformly, and adding ammonia water to adjust the pH to 9. Then 17.88g of carbon nano tubes are evenly dispersed into the solution, the temperature is raised to 75 ℃, the heat is preserved for 8 hours, black sediment is obtained, and the catalyst precursor is obtained through filtration. And (3) placing the catalyst precursor in an electrolytic tank, reducing for 7 hours in the hydrogen atmosphere generated by electrolysis, filtering after reduction, drying for 4 hours at 100 ℃, and finally placing in a nitrogen roasting furnace for roasting for 8 hours at 450 ℃ under normal pressure to obtain the catalyst A.
(2) Preparation of coconut aldehyde
400g of n-hexanol, 86.09g of methyl acrylate and 0.843g of catalyst A are added into a three-necked flask under normal pressure, the temperature is raised to 100 ℃ for reaction for 5 hours, and simultaneously, the generated methanol is separated by reactive distillation. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the catalyst A was removed by filtration, and the obtained reaction mixture was analyzed by gas chromatography, whereby the conversion of methyl acrylate was 99.2% and the cocoaldehyde selectivity was 93.5%.
[ example 2 ]
(1) Preparation of catalyst B
To 400g deionized water was added 0.5g ruthenium acetate, 0.036g NbCl 5 、0.469g Ce(NO 3 ) 3 Dissolving and stirring uniformly, and adding ammonia water to adjust the pH to 9. Then uniformly dispersing 19.99g of carbon nano tubes into the solution, heating to 50 ℃, preserving heat for 10 hours to obtain black precipitate, and filtering to obtain a catalystA precursor. And (3) placing the catalyst precursor in an electrolytic tank, reducing for 5 hours in the hydrogen atmosphere generated by electrolysis, filtering after reduction, drying for 2 hours at 120 ℃, and finally placing in a nitrogen roasting furnace for roasting for 10 hours at 350 ℃ under normal pressure to obtain the catalyst B.
(2) Preparation of coconut aldehyde
400g of n-hexanol, 168.5g of methyl acrylate and 0.843g of catalyst B are added into a three-neck flask under normal pressure, the temperature is raised to 70 ℃ for reaction for 8 hours, and simultaneously, the generated methanol is separated by reactive distillation. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the catalyst B was removed by filtration, and the obtained reaction mixture was analyzed by gas chromatography, whereby the conversion of methyl acrylate was 95.5% and the cocoaldehyde selectivity was 85.8%.
[ example 3 ]
(1) Preparation of catalyst C
To 400g of deionized water was added 0.5g of ruthenium acetate, 0.174g of NbCl 5 、0.059g Ce(NO 3 ) 3 Dissolving and stirring uniformly, and adding ammonia water to adjust the pH to 9. Then, 14.52g of carbon nano tubes are uniformly dispersed into the solution, the temperature is raised to 90 ℃, the heat is preserved for 5 hours, black sediment is obtained, and the catalyst precursor is obtained through filtration. And (3) placing the catalyst precursor in an electrolytic tank, reducing for 10 hours in the hydrogen atmosphere generated by electrolysis, filtering after reduction, drying for 6 hours at 80 ℃, and finally placing in a nitrogen roasting furnace for roasting for 5 hours at 500 ℃ under normal pressure to obtain the catalyst C.
(2) Preparation of coconut aldehyde
400g of n-hexanol, 67.41g of methyl acrylate and 1.011g of catalyst C are added into a three-neck flask under normal pressure, the temperature is raised to 150 ℃ for reaction for 3 hours, and meanwhile, the generated methanol is separated by reactive distillation. After the completion of the reaction, the reaction mixture was cooled to room temperature, and catalyst C was removed by filtration, and the obtained reaction mixture was analyzed by gas chromatography, whereby the conversion of methyl acrylate was 98.5% and the cocoaldehyde selectivity was 88.5%.
[ example 4 ]
(1) Preparation of catalyst D
To 400g deionized water was added 0.5g RuCl 3 、0.14g NbCl 5 、0.3g CeCl 3 Dissolving and stirring uniformly, and adding ammonia water to adjust the pH to 9. Then will23.53g of carbon nano tubes are uniformly dispersed in the solution, the temperature is raised to 75 ℃, the temperature is kept for 8 hours, black precipitate is obtained, and the catalyst precursor is obtained through filtration. And (3) placing the catalyst precursor in an electrolytic tank, reducing for 7 hours in the hydrogen atmosphere generated by electrolysis, filtering after reduction, drying for 4 hours at 100 ℃, and finally placing in a nitrogen roasting furnace for roasting for 8 hours at 450 ℃ under normal pressure to obtain the catalyst D.
(2) Preparation of coconut aldehyde
400g of n-hexanol, 84.26g of methyl acrylate and 0.84g of catalyst D are added into a three-necked flask under normal pressure, the temperature is raised to 100 ℃ for reaction for 5 hours, and simultaneously, the generated methanol is separated by reactive distillation. After the completion of the reaction, the reaction mixture was cooled to room temperature, and catalyst D was removed by filtration, and the obtained reaction mixture was analyzed by gas chromatography, whereby the conversion of methyl acrylate was 96.4% and the cocoanut aldehyde selectivity was 94.8%.
[ example 5 ]
(1) Preparation of catalyst E
To 400g deionized water was added 0.5g RuCl 3 、0.05g NbCl 5 、0.48g CeCl 3 Dissolving and stirring uniformly, and adding ammonia water to adjust the pH to 9. Then, 25.58g of carbon nano tubes are uniformly dispersed into the solution, the temperature is raised to 50 ℃, the temperature is kept for 10 hours, black sediment is obtained, and the catalyst precursor is obtained through filtration. And (3) placing the catalyst precursor in an electrolytic tank, reducing for 5 hours in the hydrogen atmosphere generated by electrolysis, filtering after reduction, drying for 2 hours at 120 ℃, and finally placing in a nitrogen roasting furnace for roasting for 10 hours at 350 ℃ under normal pressure to obtain the catalyst E.
(2) Preparation of coconut aldehyde
400g of n-hexanol, 168.5g of methyl acrylate and 0.843g of catalyst E are added into a three-neck flask under normal pressure, the temperature is raised to 70 ℃ for reaction for 8 hours, and meanwhile, the generated methanol is separated by reactive distillation. After the completion of the reaction, the reaction mixture was cooled to room temperature, and catalyst E was removed by filtration, and the obtained reaction mixture was analyzed by gas chromatography to give a methyl acrylate conversion of 92.6% and a cocoaldehyde selectivity of 91.8%.
[ example 6 ]
(1) Preparation of catalyst F
To 400g deionized water was added 0.5g RuCl 3 、0.24g NbCl 5 、0.059g CeCl 3 Dissolving and stirring uniformly, and adding ammonia water to adjust the pH to 9. Then, 19.99g of carbon nano tubes are uniformly dispersed into the solution, the temperature is raised to 90 ℃, the heat is preserved for 5 hours, black sediment is obtained, and the catalyst precursor is obtained through filtration. And (3) placing the catalyst precursor in an electrolytic tank, reducing for 10 hours in the hydrogen atmosphere generated by electrolysis, filtering after reduction, drying for 6 hours at 80 ℃, and finally placing in a nitrogen roasting furnace for roasting for 5 hours at 500 ℃ under normal pressure to obtain the catalyst F.
(2) Preparation of coconut aldehyde
400g of n-hexanol, 67.41g of methyl acrylate and 1.01g of catalyst F are added into a three-neck flask under normal pressure, the temperature is raised to 150 ℃ for reaction for 3 hours, and meanwhile, the generated methanol is separated by reactive distillation. After the completion of the reaction, the reaction mixture was cooled to room temperature, and catalyst F was removed by filtration, and the obtained reaction mixture was analyzed by gas chromatography, whereby the conversion of methyl acrylate was 95.4% and the cocoaldehyde selectivity was 84.9%.
Comparative example 1
A catalyst was prepared in substantially the same manner as in example 1 and n-hexanol and methyl acrylate were reacted in the presence of the catalyst to give cocoaldehyde, except that ruthenium acetate was not added in the preparation of the catalyst, and other reaction conditions were the same as in example 1. The prepared cocoanut aldehyde reaction liquid is subjected to gas chromatographic analysis, the conversion rate of methyl acrylate is 10.1%, and the cocoanut aldehyde selectivity is 50.5%.
Comparative example 2
A catalyst was prepared in substantially the same manner as in example 1 and n-hexanol and methyl acrylate were reacted in the presence of the catalyst to give coconut aldehyde, except that NbCl was not added in the preparation of the catalyst 5 Other reaction conditions were the same as in example 1. The prepared cocoanut aldehyde reaction liquid is subjected to gas chromatographic analysis, the conversion rate of methyl acrylate is 92.1%, and the cocoanut aldehyde selectivity is 89.7%.
[ comparative example 3 ]
A catalyst was prepared in substantially the same manner as in example 1 and n-hexanol and methyl acrylate were reacted in the presence of the catalyst to give cocoaldehyde, except thatNO addition of Ce (NO) in the preparation of the catalyst 3 ) 3 Other reaction conditions were the same as in example 1. The prepared cocoanut aldehyde reaction liquid is subjected to gas chromatographic analysis, the conversion rate of methyl acrylate is 93.2%, and the cocoanut aldehyde selectivity is 90.1%.
[ comparative example 4 ]
A catalyst was prepared in substantially the same manner as in example 1 and n-hexanol and methyl acrylate were reacted in the presence of the catalyst to give coconut aldehyde, except that NbCl was not added in the preparation of the catalyst 5 And Ce (NO) 3 ) 3 Other reaction conditions were the same as in example 1. The prepared reaction liquid of cocoanut aldehyde was analyzed by gas chromatography, the conversion rate of methyl acrylate was 83.2%, and the cocoanut aldehyde selectivity was 84.9%.
Comparative example 5
Referring to a catalyst prepared in substantially the same manner as in example 1 and reacting n-hexanol and methyl acrylate in the presence of the catalyst to produce cocoaldehyde, except that carbon nanotubes were replaced with silica in the preparation of the catalyst, other reaction conditions were the same as in example 1. The prepared cocoanut aldehyde reaction liquid is subjected to gas chromatographic analysis, the conversion rate of methyl acrylate is 93.1%, and the cocoanut aldehyde selectivity is 90.8%.
[ comparative example 6 ]
A catalyst was prepared in substantially the same manner as in example 1 and n-hexanol and methyl acrylate were reacted in the presence of the catalyst to give cocoaldehyde, except that the reduction of the catalyst precursor was different, specifically as follows:
(1) Preparation of the catalyst
To 400g of deionized water was added 0.5g of ruthenium acetate, 0.107g of NbCl 5 、0.293g Ce(NO 3 ) 3 Dissolving and stirring uniformly, and adding ammonia water to adjust the pH to 9. Then 17.88g of carbon nano tubes are evenly dispersed into the solution, the temperature is raised to 75 ℃, the heat is preserved for 8 hours, black sediment is obtained, and the catalyst precursor is obtained through filtration. And drying the catalyst precursor for 4 hours at the temperature of 100 ℃, and finally placing the catalyst precursor in a nitrogen roasting furnace for roasting for 8 hours at the temperature of 450 ℃ under normal pressure to prepare the catalyst.
(2) Preparation of coconut aldehyde
The prepared catalyst is reduced by introducing hydrogen at the speed of 5L/h under the pressure of 5MPa at 80 ℃ for 3h.
400g of n-hexanol, 86.09g of methyl acrylate and 0.843g of catalyst were added to a three-necked flask under normal pressure, the temperature was raised to 100℃for reaction for 5 hours, and the produced methanol was separated by reactive distillation. After the completion of the reaction, the reaction mixture was cooled to room temperature, the catalyst was removed by filtration, and the obtained reaction mixture was analyzed by gas chromatography, whereby the conversion of methyl acrylate was 94.9% and the cocoaldehyde selectivity was 95.1%.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (17)
1. A carbon nanotube-supported Ru-Nb-Ce trimetallic catalyst for the preparation of coco aldehyde, characterized in that the catalyst comprises metals Ru, nb, ce as active components, and carbon nanotubes as a support;
the mol ratio of the Ru, the Nb and the Ce of the metal is 1 (0.1-0.5) to 0.1-0.8;
in the catalyst, the mass of the carbon nano tube is 45-55 times of the total mass of metals Ru, nb and Ce;
the preparation method of the trimetallic catalyst comprises the following steps:
1) Placing metal precursors Ru salt, nb salt and Ce salt into deionized water, adding ammonia water to adjust the pH to 8-10, uniformly adding carbon nano tubes into the obtained solution after complete dissolution, and stirring and dispersing to obtain a mixture containing black precipitates;
2) Filtering the mixture obtained in the step 1) to obtain a catalyst precursor; and (3) placing the catalyst precursor in a hydrogen reducing atmosphere for reduction, filtering and drying, and roasting in an inert atmosphere to obtain the Ru-Nb-Ce trimetallic catalyst loaded by the carbon nano tube.
2. The trimetallic catalyst according to claim 1, wherein the molar ratio of the metals Ru, nb, ce is 1 (0.2-0.3): 0.4-0.6.
3. The trimetallic catalyst according to claim 1, wherein the Ru salt is one or more of ruthenium trichloride, ruthenium acetate; the Nb salt is one or more of niobium pentachloride, niobium oxalate and niobium n-propoxide; the Ce salt is one or more of cerium trichloride, cerium nitrate and cerium acetate.
4. The trimetallic catalyst according to claim 1, wherein in step 1), after adding the carbon nanotubes, the stirring dispersion conditions are: the stirring temperature is 50-90 ℃, and the stirring time is 5-10h.
5. The trimetallic catalyst according to claim 4, wherein in step 1), after adding the carbon nanotubes, the stirring dispersion conditions are: the stirring temperature is 70-80 ℃ and the stirring time is 7-8h.
6. A trimetallic catalyst according to claim 3, wherein in step 2) the reduction of the catalyst precursor is carried out in a hydrogen generator cell, the catalyst precursor being reduced by hydrogen produced by electrolysis of water.
7. The trimetallic catalyst according to claim 6, wherein the hydrogen generator electrolyzer produces hydrogen at a flow rate of 0.5-2L/min.
8. The trimetallic catalyst according to any one of claims 1 to 7, wherein in step 2), the calcination conditions are: the temperature is 350-500 ℃ and the time is 5-10h.
9. The trimetallic catalyst according to claim 8, wherein in step 2), the calcination conditions are: the temperature is 400-450 ℃ and the time is 6-8h.
10. Use of a trimetallic catalyst according to any one of claims 1 to 9 for the preparation of cocoaldehyde by the catalytic reaction of n-hexanol and methyl acrylate.
11. Use according to claim 10, wherein methyl acrylate and excess n-hexanol are reacted in the presence of a trimetallic catalyst to produce cocoaldehyde.
12. The use according to claim 11, wherein the reaction conditions are: the reaction temperature is 70-150 ℃ and the reaction time is 3-8h.
13. The use according to claim 12, wherein the reaction conditions are: the reaction temperature is 90-110 ℃ and the reaction time is 4-6h.
14. Use according to claim 11, characterized in that the molar ratio of n-hexanol to methyl acrylate is 2-5:1.
15. Use according to claim 14, wherein the molar ratio of n-hexanol to methyl acrylate is 3-4:1.
16. The use according to claim 11, wherein the trimetallic catalyst is added in the reaction in an amount of 0.5-1.5% by mass of methyl acrylate.
17. The use according to claim 16, wherein the trimetallic catalyst is added in the reaction in an amount of 0.8-1.2% by mass of methyl acrylate.
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