CN105854951B - A kind of preparation of anti-oxidant nano-copper base catalyst and application method - Google Patents
A kind of preparation of anti-oxidant nano-copper base catalyst and application method Download PDFInfo
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- CN105854951B CN105854951B CN201610295110.4A CN201610295110A CN105854951B CN 105854951 B CN105854951 B CN 105854951B CN 201610295110 A CN201610295110 A CN 201610295110A CN 105854951 B CN105854951 B CN 105854951B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000010949 copper Substances 0.000 title claims abstract description 46
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 title claims description 16
- 230000003078 antioxidant effect Effects 0.000 title claims description 16
- 235000006708 antioxidants Nutrition 0.000 title claims description 16
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 49
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 44
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 44
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000005642 Oleic acid Substances 0.000 claims abstract description 44
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 44
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims abstract description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 4
- 238000005253 cladding Methods 0.000 claims abstract 2
- 239000003921 oil Substances 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 241000196324 Embryophyta Species 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000011949 solid catalyst Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000000346 nonvolatile oil Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 claims 1
- 244000283207 Indigofera tinctoria Species 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 claims 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- 238000011017 operating method Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 2
- 235000021313 oleic acid Nutrition 0.000 description 33
- 238000006555 catalytic reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 235000019197 fats Nutrition 0.000 description 5
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 4
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229960004488 linolenic acid Drugs 0.000 description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000003407 synthetizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of methods for making and using sames of nano-copper base catalyst suitable for the production of high-purity oleic acid, and the preparation method is with CuCl2·2H2O solution is that raw material restores to obtain Nanometer Copper-cuprous oxide Cu-Cu through reducing agent under the processing of cetyl trimethylammonium bromide CTAB solution and sodium hydroxide solution2O obtains the strong nano-copper base catalyst of inoxidizability finally by the ethanol solution cladding of package oil plant；It is applied to the production of oleic acid, conveniently obtains high-purity oleic acid product；Nano-copper base catalyst activity of the invention is higher, and catalytic efficiency is fast, and in air with it is not oxidizable under hot conditions, long service life facilitates storage and carrying, saves the production cost of enterprise.
Description
Technical field
The present invention relates to the production technical field of oleic acid more particularly to it is a kind of suitable for high-purity oleic acid production it is anti-oxidant
The methods for making and using same of nano-copper base catalyst.
Background technique
With to environmental protection attention and petroleum resources it is in short supply, produce various soap products, each by raw material of grease
The oil and fat chemical industry of kind fatty acid and derivative of fatty acid is flourished.Oleic acid is the important original in oil and fat chemical field
Material, is mainly derived from nature.Oleic acid is mainly present in animal and plant fat in the form of its glyceride.Oleic acid content is high
Oleic acid can be obtained by saponification, acidification separation in grease.Currently, oil and fat chemical enterprise, China production industrial oleic acid product its
It is the mixture of palmitinic acid C16:0, stearic acid C18:0, oleic acid C18:1, linoleic acid C18:2, linolenic acid C18:3 etc. in fact, wherein
Oleic acid C18:1 content only has 30% -40%, and purity is not high, constrains the increased quality of oleic acid downstream product.All the time, domestic
Oil and fat chemical enterprise cannot produce the high-purity oleic acid of high-quality, market is occupied by external product for a long time.
High-purity oleic acid refers generally to the oleic acid that C18:1 content is more than 70%, and stability is good, non-stimulated to skin.Safety
Height has excellent Wuli-Shili-Renli system approach, high-purity oleic acid derivatives can also be processed into, so high-purity oleic acid can be used as life
The main foundation raw material for producing a variety of fine chemicals such as plasticizer, detergent and surfactant is more suitable for medicine, makeup
The application in the fields such as product, bioengineering, plays an important role in national economy.
Linolenic acid therein, linoleic content can be effectively reduced by selective catalytic hydrogenation in industrial oleic acid, mentions
It is unobvious while high oleic acid content to increase stearic content, there is very important industrial significance.Therefore it is suitable to develop
It is imperative that effective catalyst carries out industrial oleic acid selective hydrogenation.
Nano transition metal oxides (MOs) are a kind of novel functional materials, with its unique physical and chemical performance, extensively
Applied to microelectronics, photoelectricity in the fields such as chemical industry and environmental protection, has obtained extensive concern and research.In numerous nanometers of mistakes
It crosses in metal oxide (MOs), nano-copper base oxide (nanometer Cu2O) it is a kind of novel functional material, is led in scientific research
All there is good potential using value, such as photoelectric material, sensor and catalysis material etc. in domain and industrial application.
Traditional nanometer Cu-Cu2O catalyst, since easily oxidation becomes cupric to its particle in air, after oxidation
It is originally that catalytic activity substantially reduces to catalyst, in catalytic reaction process, needs a large amount of Cu-Cu2O catalyst could be completed
Catalysis reaction to product；Meanwhile people store Cu-Cu by sealing or vacuum2O catalyst, but since itself is stored
The leakproofness of device, taking and transporting very inconvenient for the catalyst itself, needs the operation ability cumbersome by multistep
It completes, it is time-consuming and laborious, substantially increase the production cost of enterprise.
Summary of the invention
In view of the above problems, it is high that it is an object of that present invention to provide a kind of catalytic activity, conveniently recycles, antioxygen
The methods for making and using same of the high nano-copper base catalyst for being suitable for the production of high-purity oleic acid of the property changed.
In order to achieve the above object, The technical solution adopted by the invention is as follows: a kind of anti-oxidant nano-copper base catalyst
Preparation method, the preparation method is with CuCl2·2H2O solution is raw material, in cetyl trimethylammonium bromide CTAB solution
Under the processing of sodium hydroxide solution, restore to obtain Nanometer Copper-cuprous oxide Cu-Cu through reducing agent2O, finally by package oil
The ethanol solution of material coats, and obtains the strong nano-copper base catalyst of inoxidizability.
The detailed preparation method of the present invention includes following operation:
1) CuCl for being 0.5~5mol/L by concentration2·2H2It is 2.5~10 mol/L's that O solution is added dropwise to concentration dropwise
It in NaOH solution, is vigorously stirred at 40~90 DEG C, forms blue brown solution.
2) the cetyl front three that concentration is 0.1~1.5mol/L is slowly added dropwise into indigo plant brown solution made from step 1)
Base ammonium bromide CTAB solution, continuation are vigorously stirred 0.5~5 h at 40~90 DEG C.
3) reducing agent is added into solution made from step 2, the dosage of reducing agent is 0.01~0.72 in every liter of solution
Mol is vigorously stirred 0.5~5h, is transferred in reaction kettle, at 100~280 DEG C, reacts 10~30 h, and it is brick-red heavy to obtain
It forms sediment: Nanometer Copper-cuprous oxide Cu-Cu2O。
4) into alcohol solvent be added package oil plant preparation, wherein package oil plant and ethyl alcohol amount ratio be 3~5:5~
20, by Nanometer Copper obtained in step 3)-cuprous oxide Cu-Cu2The alcoholic solution of above-mentioned package oil plant is added in O, at 40~60 DEG C
Under be vigorously stirred 1~4 h of reaction.
5) mixed liquor in step 4) is naturally cooled into room temperature, be centrifuged, obtained solid product is first with distillation
Water washing 3~5 times, then with ethanol washing 3~5 times, dry 3~12h under vacuum conditions, obtain catalyst prod.
Wherein CuCl2·2H2O solution, NaOH solution, cetyl trimethylammonium bromide CTAB solution three dosage
Than for 1~15:4~20:2~20.
Reducing agent in step 3) of the present invention is glucose, sucrose, Vc, KBH4、NaH2PO2In hydrazine hydrate
Any one.
Package oil plant in step 4) of the present invention is appointing in palmitinic acid, stearic acid, fixed oil and polyethylene glycol
What is a kind of.
Nanometer Copper-cuprous oxide Cu-Cu in step 4) solution of the present invention2O dosage is 0.08~0.5g/mL.
Application of the anti-oxidant nano-copper base catalyst of method production of the invention when preparing oleic acid, detailed operation
Method is as follows:
1) industrial oleic acid is added in reaction kettle, adds 0.1~10 % that quality is reactant industrial oleic acid gross mass
Anti-oxidant nano-copper base catalyst, reaction temperature be 150~300 DEG C, logical hydrogen makes 1.2~3.5 Mpa of pressure, stirs
Rate is mixed as under the conditions of 200~1000 rpm, the reaction time is 1~6 h, obtains hydrogenation products.
2) product is filtered, obtains solid catalyst and oleic acid product, wherein the solid catalyst filtered out is followed
Ring uses.
The present invention has the advantages that production method of the invention is by nanometer Cu-Cu2O dispersion is solid packet at normal temperature
It wraps up in oil plant, on the one hand can prevent nanometer Cu and Cu2O oxidation by air, consequently facilitating storage and transport, on the other hand may be used
To reduce nanometer Cu and Cu2Interaction force between O powder enhances dispersibility of the catalyst in grease reactant, in turn
Improve catalytic activity.
Specific embodiment
The present invention is described in further detail With reference to embodiment.
Test material and catalyst used in following embodiments are unless otherwise noted the conventional examination bought on the market
Agent material and catalyst.
Embodiment 1: a kind of preparation method of anti-oxidant nano-copper base catalyst:
1) Nanometer Copper-cuprous oxide Cu-Cu2The preparation of O: hydro-thermal method synthetizing nano-copper-cuprous oxide Cu-Cu is used2O, will
20 mL concentration are the CuCl of 1 mol/L2·2H2O solution is added dropwise to dropwise in the NaOH solution that 80 mL concentration are 5 mol/L,
It is vigorously stirred at 50 DEG C, forms blue brown solution；
2) the cetyl trimethylammonium bromide CTAB solution that 40 mL concentration are 0.25 mol/L is then added dropwise, continues
1 h is vigorously stirred at 50 DEG C；
3) 20 mmol glucose are added, is vigorously stirred 1 h, is transferred in 200 mL reaction kettles, hot water 24 at 140 DEG C
H obtains brick-red precipitated nanocrystals copper-cuprous oxide Cu-Cu2O；
4) in 100mL ethyl alcohol, 30 mL is added and wrap up oil plant stearic acid, are vigorously stirred down, by Nanometer Copper-cuprous oxide
Cu-Cu2Above-mentioned stearic alcoholic solution is added in 30 g of O powder, and 1 h is vigorously stirred at 50 DEG C；
5) room temperature is then naturally cooled to, solution is taken out, is centrifuged, is first washed with distilled water 4 times, then use ethyl alcohol
Washing 4 times, drying 5 h under vacuum conditions is to obtain catalyst of nano-copper-cuprous oxide Cu-Cu of stearic acid package2O。
Embodiment 2: it in the case where the preparation condition of catalyst is identical with embodiment 1, will only be gone back in preparation method
Former agent glucose is changed to sucrose, obtains anti-oxidant nano-copper base catalyst.
Embodiment 3: it in the case where the preparation condition of catalyst is identical with embodiment 1, will only be gone back in preparation method
Former agent glucose is changed to KBH4, oil plant select fixed oil, obtain anti-oxidant nano-copper base catalyst.
Embodiment 4: it in the case where the preparation condition of catalyst is identical with embodiment 1, will only be gone back in preparation method
Former agent glucose is changed to NaH2PO2, oil plant select palmitinic acid, obtain anti-oxidant nano-copper base catalyst.
Embodiment 5:, only will package oil plant tristearin in the case where the preparation condition of catalyst is identical with embodiment 1
Acid is changed to polyethylene glycol, obtains anti-oxidant nano-copper base catalyst.
Embodiment 6: the anti-oxidant nano-copper base catalyst produced in embodiment 1-5 is applied to the life of high-purity oleic acid
It produces, specific production method is as follows:
80 g industrial oleic acids are added in reaction kettle, add 4.0 %'s that quality is reactant industrial oleic acid gross mass
Anti-oxidant nano-copper base catalyst is 190 DEG C in reaction temperature, and logical hydrogen makes 1 Mpa of pressure, and stirring rate is 600 rpm
Under the conditions of, the reaction time is 1 h, obtains hydrogenation products.Variation is formed with fatty acid as examination index, the catalysis of gained catalyst
Performance is as shown in table 1:
The anti-oxidant nano-copper base catalyst of table 1 prepares the catalytic performance of high-purity oleic acid
As seen from the above table: production of the invention obtains ability catalyst catalytic effect with higher for the processing of oleic acid,
After catalytic hydrogenation reaction, the C18:1 amount (wt%) after the catalysis reaction in final oleic acid product in oleic acid is greatly improved,
And the amount (wt%) of the C18:2 after catalysis reaction in oleic acid substantially reduces, and the C18:3 after catalysis reaction in oleic acid is almost
Catalysis reaction is completed, good practical effect.
Embodiment 7: comparing test for catalyst obtained in the embodiment of the present invention 1, by itself and catalysis on the market
Agent is handled in air, and result is as shown in the table:
As seen from the above table: after catalyst of the invention carries out placement and high-temperature process in air, the catalyst of itself
Activity biggish change does not occur, compared to the conventional metallic catalyst bought on the market, stability is higher, market
On conventional catalyst after having been treated, activity substantially reduces；At the same time, being further added by catalyst amount is that energy is further
Raising end reaction obtain the yield of C18:1 in product oleic acid, it is excessive but since the production cost of catalyst itself is higher
Anti-oxidant nano-copper base catalyst the yields of final products is promoted unobvious, and cause a large amount of wastes of catalyst.
Embodiment 8: the production method in the embodiment of the present invention 1 is compared into test, in other conditions and embodiment 1
In the case where constant, obtained catalyst and catalysis reaction is carried out to oleic acid, obtained result is as shown in the table:
As seen from the above table: when producing nano-copper base catalyst, the amount ratio of each solution is wrapped up in liquid method of the invention
The amount ratio of Nanometer Copper-cuprous oxide dosage and package oil plant can influence the performance of final products, when Nanometer Copper-
When the dosage of cuprous oxide is very few, the catalytic performance of final products works as CuCl in its reaction raw materials compared to decline2·2H2O is molten
When liquid excess, certain decline is also had occurred in the catalytic performance of final products.
It should be noted that above-mentioned is only presently preferred embodiments of the present invention, protection model not for the purpose of limiting the invention
It encloses, any combination or equivalents made on the basis of the above embodiments all belong to the scope of protection of the present invention.
Claims (3)
1. a kind of application method of the nano-copper base catalyst suitable for the production of high-purity oleic acid, which is characterized in that described to be applicable in
In high-purity oleic acid production nano-copper base catalyst preparation method with CuCl2·2H2O solution is raw material, in cetyl three
Under the processing of methyl bromide ammonium CTAB solution and sodium hydroxide solution, restore to obtain Nanometer Copper-cuprous oxide Cu- through reducing agent
Cu2O obtains the strong nano-copper base catalyst of inoxidizability finally by the ethanol solution cladding of package oil plant；By above-mentioned antioxygen
Change nano-copper base catalyst to be applied to prepare the oleic acid of high-purity C 18:1 amount (wt%)；
The preparation method includes following operation:
1) CuCl for being 0.5~5mol/L by concentration2·2H2O solution is added dropwise to the NaOH that concentration is 2.5~10 mol/L dropwise
It in solution, is vigorously stirred at 40~90 DEG C, forms blue brown solution；
2) the cetyl trimethyl bromine that concentration is 0.1~1.5mol/L is slowly added dropwise into indigo plant brown solution made from step 1)
Change ammonium CTAB solution, continuation is vigorously stirred 0.5~5 h at 40~90 DEG C；
3) reducing agent is added into solution made from step 2, the dosage of reducing agent is 0.01~0.72 mol in every liter of solution,
It is vigorously stirred 0.5~5h, is transferred in reaction kettle, at 100~280 DEG C, 10~30 h is reacted, obtains brick-red precipitating: receiving
Rice copper-cuprous oxide Cu-Cu2O；
4) package oil plant preparation is added into alcohol solvent, wherein the amount ratio of package oil plant and ethyl alcohol is 3~5:5~20, it will
Nanometer Copper obtained in step 3)-cuprous oxide Cu-Cu2The alcoholic solution of above-mentioned package oil plant is added in O, at 40~60 DEG C acutely
It is stirred to react 1~4 h, package oil plant is any one of palmitinic acid, stearic acid, fixed oil and polyethylene glycol；
5) mixed liquor in step 4) is naturally cooled into room temperature, be centrifuged, obtained solid product is first with distillation washing
It washs 3~5 times, then with ethanol washing 3~5 times, dries 3~12h under vacuum conditions, obtain catalyst prod；
Wherein CuCl2·2H2O solution, NaOH solution, cetyl trimethylammonium bromide CTAB solution three amount ratio be 1
~15:4~20:2~20；
It is applied to the anti-oxidant nano-copper base catalyst that above-mentioned preparation method produces to prepare high-purity oleic acid, operating method is such as
Under:
1) industrial oleic acid is added in reaction kettle, adds the anti-of 0.1~10 % that quality is reactant industrial oleic acid gross mass
Oxidation nanometer copper-based catalysts are 150~300 DEG C in reaction temperature, and logical hydrogen makes 1.2~3.5 Mpa of pressure, stirring speed
Under the conditions of rate is 200~1000 rpm, the reaction time is 1~6 h, obtains hydrogenation products；
2) product is filtered, obtains solid catalyst and high-purity oleic acid product, wherein the solid catalyst filtered out is followed
Ring uses.
2. the application method suitable for the nano-copper base catalyst of high-purity oleic acid production as described in claim 1, feature
It is, the reducing agent is glucose, sucrose, Vc, KBH4、NaH2PO2With any one in hydrazine hydrate.
3. the application method suitable for the nano-copper base catalyst of high-purity oleic acid production as described in claim 1, feature
It is, Nanometer Copper-cuprous oxide Cu-Cu in solution2O dosage is 0.08~0.5g/mL.
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| CN111595918A (en) * | 2020-05-26 | 2020-08-28 | 信阳师范学院 | Octahedron Cu-Cu2Preparation method of O composite material |
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| CN101722314A (en) * | 2009-11-20 | 2010-06-09 | 云南大学 | Method for preparing Cu2O-Cu composite microsphere by adopting bean flour as template |
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