CN108970631A - A kind of nano-copper base catalyst and preparation method thereof - Google Patents
A kind of nano-copper base catalyst and preparation method thereof Download PDFInfo
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- CN108970631A CN108970631A CN201810849431.3A CN201810849431A CN108970631A CN 108970631 A CN108970631 A CN 108970631A CN 201810849431 A CN201810849431 A CN 201810849431A CN 108970631 A CN108970631 A CN 108970631A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 29
- 239000010949 copper Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000000694 effects Effects 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 238000011068 loading method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 21
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims abstract description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 8
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 34
- 238000010792 warming Methods 0.000 claims description 29
- 238000004321 preservation Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- 235000019441 ethanol Nutrition 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 229960004756 ethanol Drugs 0.000 claims description 17
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 abstract description 23
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 abstract description 20
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 abstract description 20
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 abstract description 20
- 239000005642 Oleic acid Substances 0.000 abstract description 20
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 abstract description 20
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 abstract description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000002091 nanocage Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 5
- 235000019197 fats Nutrition 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000006243 chemical reaction Methods 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000001965 increasing 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- -1 Supported Co Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 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
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 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
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
Abstract
The invention discloses a kind of nano-copper base catalysts and preparation method thereof, belong to chemical field.The present invention is using methylimidazole and cabaltous nitrate hexahydrate as raw material mixed calcining, form the nanocages lattice of Porous hollow, add six nitric hydrate copper, by copper ion doped into lattice, form the catalyst activity body of coordination, enhancing catalysis produces oxygen activity in optical drive water oxygen, improves catalytic efficiency；The present invention by calcining, obtains the catalyst precursor of doped graphite phase carbon nitride, improves oleic acid supported catalyst amount, reduce the usage amount of catalyst using dicyanodiamine, ammonium metavanadate as raw material；The present invention is that raw material forms magnetic loading object with Iron(III) chloride hexahydrate, anhydrous sodium acetate, 1,6- hexamethylene diamine etc., has superparamagnetic property, catalyst can be recycled and reused, improves catalyst service efficiency.The present invention solves the problems, such as that the catalytic activity of current catalyst is low, dosage is big.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of nano-copper base catalyst and preparation method thereof.
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, the industrial oleic acid product of oil and fat chemical enterprise production is in fact
The mixture of palmitinic acid C16:0, stearic acid C18:0, oleic acid C18:1, linoleic acid C18:2, linolenic acid C18:3 etc., 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, oil and fat chemical
Enterprise cannot produce the high-purity oleic acid of high-quality, and market is occupied by other products 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 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) 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.Tradition
Nanometer Cu-Cu2O catalyst, due to its particle in air easily oxidation become cupric, the catalyst after oxidation its be originally
Catalytic activity substantially reduces, and in catalytic reaction process, needs a large amount of Cu-Cu2O catalyst that could complete the catalysis to product
Reaction；Therefore a kind of catalytic activity height is produced, the low nano-copper base catalyst of dosage has very big market prospects.
Summary of the invention
The technical problems to be solved by the invention: for current catalyst catalytic activity is low, problem that dosage is big, provide
A kind of nano-copper base catalyst and preparation method thereof.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of nano-copper base catalyst includes catalyst activity body, catalyst precursor, magnetic loading object；
The preparation method of the catalyst activity body, includes the following steps:
(1) take methylimidazole 1 ~ 3:10 in mass ratio ~ 20 be added methanol be stirred, obtain solution A, take cabaltous nitrate hexahydrate by
2 ~ 4:25 of mass ratio ~ 35 is added methanol and is stirred, and obtains solution B, takes solution A 4 ~ 7:2 in mass ratio ~ 4 that solution B is added, in 45 ~
50 DEG C are stirred, and stand, and centrifugation takes precipitating to wash through methanol, dry, obtain dried object, dried object is taken to keep the temperature, be cooled to room
Temperature obtains cooled material；
(2) it takes cooled material 1 ~ 4:50 in mass ratio ~ 60 that ethyl alcohol is added to be stirred, adds six water of cooled material quality 7 ~ 10%
Copper nitrate is closed, 2 ~ 3h is stirred, is centrifuged, precipitating a is taken to wash through dehydrated alcohol, it is dry, it is cold in 350 ~ 400 DEG C of calcining 1 ~ 2h
But to room temperature to get catalyst activity body.
The heat-retaining condition of dried object in the step (1) are as follows: in 400 ~ 450 DEG C of 2 ~ 3h of heat preservation, controlling heating rate is 2
℃/min。
The preparation method of the catalyst precursor, includes the following steps:
It takes dicyanodiamine in quartzy Noah's ark, is passed through nitrogen protection, be warming up to 280 ~ 300 DEG C of 2 ~ 3h of heat preservation, then it is warming up to 500 ~
55 DEG C of 3 ~ 4 h of calcining, obtain calcined material, take calcined material 3 ~ 5:0.2 in mass ratio ~ 0.4:20 ~ 30 that ammonium metavanadate, deionization is added
Water, 20 ~ 30min of magnetic agitation are warming up to 70 ~ 80 DEG C and are stirred, dry, grind, and cross 80 meshes, collect sieving
Grain, is passed through nitrogen protection, and sieving particle heat-insulating, calcining are cooled to room temperature to get catalyst precursor.
The heat preservation of the sieving particle, calcination condition are as follows: in 300 ~ 350 DEG C of 1 ~ 2h of heat preservation, then be warming up to 500 ~ 550 DEG C and forge
Burn 3 ~ 4h.
The preparation method of the magnetic loading object, includes the following steps:
It takes Iron(III) chloride hexahydrate 1 ~ 3:2 in mass ratio ~ 5:5 ~ 7 that anhydrous sodium acetate, 1,6- hexamethylene diamine is added, obtains mixture, take
Ethylene glycol mixing is added in mixture 1 ~ 3:5 in mass ratio ~ 8, is stirred in 25 ~ 30 DEG C, then be warming up to 150 ~ 200 DEG C of heat preservations,
Magnet attracts, and magnet attraction is taken to wash through deionized water, dehydrated alcohol, dry to get magnetic loading object.
A kind of preparation method of nano-copper base catalyst, includes the following steps:
According to the mass fraction, 5 ~ 8 parts of catalyst activity bodies, 1 ~ 3 part of catalyst precursor, 7 ~ 10 parts of magnetic loading objects, 50 ~ 70 are taken
Part dehydrated alcohol mixing, 20 ~ 30min of ultrasonic disperse obtain ultrasonic liquid, take ultrasonic liquid 7 ~ 9:4 in mass ratio ~ 6 that sodium borohydride is added
Ethanol solution is stirred, and magnet attracts, and takes magnet attraction a through deionized water, ethanol washing, dry to get nano-copper base
Catalyst.
It is described to be stirred condition are as follows: to be stirred 1 ~ 2h in 25 ~ 30 DEG C.
The present invention is compared with other methods, and advantageous effects are:
(1) for the present invention using methylimidazole and cabaltous nitrate hexahydrate as raw material mixed calcining, the nanocages for forming Porous hollow are brilliant
Lattice, porous three-dimensional hollow frame provide reactivity site abundant for catalysis reaction, add six nitric hydrate copper, will
It is copper ion doped to form the catalyst activity body of coordination into lattice, it shows preferably to be catalyzed in oleic acid dehydrogenation oxidation and live
Property passes through Co in catalytic process3O4The photohole that the CuO itself of the photohole and formation that are transferred on CuO in valence band is generated
Oxidative dehydrogenation together, while heterojunction structure existing for catalyst activity body strengthens charge hole by forming inherent electron field
Separation, enhancing catalysis produces oxygen activity in optical drive water oxygen, improves catalytic efficiency；
(2) present invention, by calcining, obtains the catalyst of doped graphite phase carbon nitride using dicyanodiamine, ammonium metavanadate as raw material
Presoma has the pi-conjugated structure of two-dimensional surface similar to graphite, transition by transition metal oxides such as Supported Co, copper
Metal species may be combined by way of being similar to metal M-N chemical bond between graphite phase carbon nitride matrix, form chemistry
The vanadium of coordinate bond, introducing adds hydroxide to have excellent redox catalysis performance, while hydrophobic class graphite conjugation oleic acid
Planar structure is conducive to adsorb and activate oleic acid, increases the lewis acidic active site of catalyst surface, improves oleic acid load
Catalytic amount reduces the usage amount of catalyst；
(3) present invention is that raw material forms magnetic loading object with Iron(III) chloride hexahydrate, anhydrous sodium acetate, 1,6- hexamethylene diamine etc., will
Less amino group modification is formed and is chemically bonded to magnetic particle surface, N and transition metal particles, preferable fixed catalyst
In nanoparticle, prevent the loss of catalyst activity substance with react in particle aggregation, while surface have more road
Lewis acid active site, being formed, there is sour characteristic to have the difunctional magnetic loading object for adding hydrogen effect again, pass through the activity of load
Transition metal particles are preferably dispersed in carrier surface, so that increasing with the reaction interface of contact catalytic specie, improve catalysis
Activity, while its saturation induction density with higher, and there is superparamagnetic property, catalyst can be carried out to recycling weight
It is multiple to utilize, improve catalyst service efficiency.
Specific embodiment
Catalyst activity body: (1) taking methylimidazole 1 ~ 3:10 in mass ratio ~ 20 that methanol is added, it is stirred 15 ~
20min obtains solution A, takes cabaltous nitrate hexahydrate 2 ~ 4:25 in mass ratio ~ 35 that methanol is added, is stirred 10 ~ 20min, obtains solution
B takes solution A 4 ~ 7:2 in mass ratio ~ 4 that solution B is added, and 20 ~ 30min is stirred in 45 ~ 50 DEG C, stands 36 ~ 72h, is centrifuged,
Take precipitating to wash through methanol, it is dry, obtain dried object, take dried object in 400 ~ 450 DEG C of 2 ~ 3h of heat preservation, control heating rate for 2 DEG C/
Min is cooled to room temperature, and obtains cooled material；
(2) take cooled material 1 ~ 4:50 in mass ratio ~ 60 be added ethyl alcohol, be stirred 5 ~ 10min, add cooled material quality 7 ~
10% six nitric hydrate copper, are stirred 2 ~ 3h, centrifugation, and precipitating a is taken to wash through dehydrated alcohol, dry, forge in 350 ~ 400 DEG C
1 ~ 2h is burnt, is cooled to room temperature to get catalyst activity body.
Catalyst precursor: taking dicyanodiamine in quartzy Noah's ark, be passed through nitrogen protection, is warming up to 280 ~ 300 DEG C of heat preservations 2
~ 3h, then 500 ~ 550 DEG C of 3 ~ 4 h of calcining are warming up to, calcined material is obtained, calcined material 3 ~ 5:0.2 in mass ratio ~ 0.4:20 ~ 30 is taken to be added
Ammonium metavanadate, deionized water, 20 ~ 30min of magnetic agitation are warming up to 70 ~ 80 DEG C and are stirred 3 ~ 5h, dry, grind, mistake
80 meshes collect sieving particle, are passed through nitrogen protection, will sieving particle in 300 ~ 350 DEG C of 1 ~ 2h of heat preservation, then be warming up to 500 ~
550 DEG C of 3 ~ 4h of calcining, are cooled to room temperature to get catalyst precursor.
Magnetic loading object: take Iron(III) chloride hexahydrate 1 ~ 3:2 in mass ratio ~ 5:5 ~ 7 be added anhydrous sodium acetate, 1,6- oneself two
Amine obtains mixture, takes mixture 1 ~ 3:5 in mass ratio ~ 8 that ethylene glycol mixing is added, is stirred 1 ~ 3h in 25 ~ 30 DEG C, then rise
Temperature to 150 ~ 200 DEG C of 8 ~ 10h of heat preservation, magnet attracts, and takes magnet attraction to wash 3 ~ 5 times through deionized water, dehydrated alcohol, does
It is dry to get magnetic loading object.
A kind of preparation method of nano-copper base catalyst, includes the following steps:
According to the mass fraction, 5 ~ 8 parts of catalyst activity bodies, 1 ~ 3 part of catalyst precursor, 7 ~ 10 parts of magnetic loading objects, 50 ~ 70 are taken
Part dehydrated alcohol mixing, 20 ~ 30min of ultrasonic disperse obtain ultrasonic liquid, take ultrasonic liquid 7 ~ 9:4 in mass ratio ~ 6 that concentration is added and are
The ethanol solution of sodium borohydride of 0.14mol/L is stirred 1 ~ 2h in 25 ~ 30 DEG C, and magnet attracts, and magnet attraction a is taken to be gone
Ionized water, ethanol washing, it is dry to get nano-copper base catalyst.
Embodiment 1
Catalyst activity body: (1) it takes methylimidazole 1:10 in mass ratio that methanol is added, is stirred 15min, obtains solution A, take
Methanol is added in cabaltous nitrate hexahydrate 2:25 in mass ratio, is stirred 10min, obtains solution B, and solution A 4:2 in mass ratio is taken to be added
Solution B is stirred 20min in 45 DEG C, stands 36h, and centrifugation takes precipitating to wash through methanol, dry, obtains dried object, takes drying
Object is 2 DEG C/min in 400 DEG C of heat preservation 2h, control heating rate, is cooled to room temperature, obtains cooled material；
(2) it takes cooled material 1:50 in mass ratio that ethyl alcohol is added, is stirred 5min, add six hydration nitre of cooled material quality 7%
Sour copper is stirred 2h, centrifugation, and precipitating a is taken to wash through dehydrated alcohol, dry, in 350 DEG C of calcining 1h, be cooled to room temperature to get
Catalyst activity body.
Catalyst precursor: taking dicyanodiamine in quartzy Noah's ark, be passed through nitrogen protection, is warming up to 280 DEG C of heat preservation 2h, then
500 DEG C of calcining 3h are warming up to, calcined material is obtained, take calcined material 3:0.2:20 in mass ratio that ammonium metavanadate, deionized water, magnetic force is added
20min is stirred, 70 DEG C is warming up to and is stirred 3h, it is dry, it grinds, crosses 80 meshes, collect sieving particle, be passed through nitrogen guarantor
Shield by sieving particle in 300 DEG C of heat preservation 1h, then is warming up to 500 DEG C of calcining 3h, is cooled to room temperature to get catalyst precursor.
Magnetic loading object: it takes Iron(III) chloride hexahydrate 1:2:5 in mass ratio that anhydrous sodium acetate, 1,6- hexamethylene diamine is added, obtains
Mixture, take mixture 1:5 in mass ratio be added ethylene glycol mixing, be stirred 1h in 25 DEG C, then be warming up to 150 DEG C heat preservation 8 ~
10h, magnet attract, and magnet attraction is taken to wash 3 times through deionized water, dehydrated alcohol, dry to get magnetic loading object.
A kind of preparation method of nano-copper base catalyst, includes the following steps:
According to the mass fraction, 5 parts of catalyst activity bodies, 1 part of catalyst precursor, 7 parts of magnetic loading objects, 50 parts of dehydrated alcohols are taken
Mixing, ultrasonic disperse 20min obtain ultrasonic liquid, take ultrasonic liquid 7:4 in mass ratio that the sodium borohydride that concentration is 0.14mol/L is added
Ethanol solution, is stirred 1h in 25 DEG C, and magnet attracts, and takes magnet attraction a through deionized water, ethanol washing, it is dry to get
Nano-copper base catalyst.
Embodiment 2
Catalyst activity body: (1) it takes methylimidazole 2:15 in mass ratio that methanol is added, is stirred 18min, obtains solution A, take
Methanol is added in cabaltous nitrate hexahydrate 3:30 in mass ratio, is stirred 15min, obtains solution B, and solution A 6:3 in mass ratio is taken to be added
Solution B is stirred 25min in 47 DEG C, stands 50h, and centrifugation takes precipitating to wash through methanol, dry, obtains dried object, takes drying
Object is 2 DEG C/min in 430 DEG C of heat preservation 2.5h, control heating rate, is cooled to room temperature, obtains cooled material；
(2) it takes cooled material 3:55 in mass ratio that ethyl alcohol is added, is stirred 7min, add six hydration nitre of cooled material quality 9%
Sour copper is stirred 2.5h, centrifugation, and precipitating a is taken to wash through dehydrated alcohol, dry, in 370 DEG C of calcining 1.5h, is cooled to room temperature,
Up to catalyst activity body.
Catalyst precursor: taking dicyanodiamine in quartzy Noah's ark, be passed through nitrogen protection, is warming up to 290 DEG C of heat preservation 2.5h,
It is warming up to 510 DEG C of calcining 3.5h again, obtains calcined material, takes calcined material 4:0.3:25 in mass ratio that ammonium metavanadate, deionized water is added,
Magnetic agitation 25min is warming up to 75 DEG C and is stirred 4h, dry, grinds, and crosses 80 meshes, collects sieving particle, is passed through nitrogen
Gas shielded by sieving particle in 330 DEG C of heat preservation 1.5h, then is warming up to 520 DEG C of calcining 3.5h, is cooled to room temperature to get catalyst
Presoma.
Magnetic loading object: it takes Iron(III) chloride hexahydrate 2:4:6 in mass ratio that anhydrous sodium acetate, 1,6- hexamethylene diamine is added, obtains
Mixture takes mixture 2:6 in mass ratio that ethylene glycol mixing is added, is stirred 2h in 28 DEG C, then be warming up to 180 DEG C of heat preservations
9h, magnet attract, and magnet attraction is taken to wash 4 times through deionized water, dehydrated alcohol, dry to get magnetic loading object.
A kind of preparation method of nano-copper base catalyst, includes the following steps:
According to the mass fraction, 7 parts of catalyst activity bodies, 2 parts of catalyst precursors, 8 parts of magnetic loading objects, 60 parts of dehydrated alcohols are taken
Mixing, ultrasonic disperse 25min obtain ultrasonic liquid, take ultrasonic liquid 8:5 in mass ratio that the sodium borohydride that concentration is 0.14mol/L is added
Ethanol solution is stirred 1.5h in 28 DEG C, and magnet attracts, and takes magnet attraction a through deionized water, ethanol washing, dries, i.e.,
Obtain nano-copper base catalyst.
Embodiment 3
Catalyst activity body: (1) it takes methylimidazole 3:20 in mass ratio that methanol is added, is stirred 20min, obtains solution A, take
Methanol is added in cabaltous nitrate hexahydrate 4:35 in mass ratio, is stirred 20min, obtains solution B, and solution A 7:4 in mass ratio is taken to be added
Solution B is stirred 30min in 50 DEG C, stands 72h, and centrifugation takes precipitating to wash through methanol, dry, obtains dried object, takes drying
Object is 2 DEG C/min in 450 DEG C of heat preservation 3h, control heating rate, is cooled to room temperature, obtains cooled material；
(2) it takes cooled material 4:60 in mass ratio that ethyl alcohol is added, is stirred 10min, adds six hydrations of cooled material quality 10%
Copper nitrate is stirred 3h, centrifugation, and precipitating a is taken to wash through dehydrated alcohol, dry, in 400 DEG C of calcining 2h, is cooled to room temperature, i.e.,
Obtain catalyst activity body.
Catalyst precursor: taking dicyanodiamine in quartzy Noah's ark, be passed through nitrogen protection, is warming up to 300 DEG C of heat preservation 3h, then
550 DEG C of 4 h of calcining are warming up to, calcined material is obtained, take calcined material 5:0.4:30 in mass ratio that ammonium metavanadate, deionized water, magnetic is added
Power stirs 30min, is warming up to 80 DEG C and is stirred 5h, dry, grinds, and crosses 80 meshes, collects sieving particle, is passed through nitrogen
Protection by sieving particle in 350 DEG C of heat preservation 2h, then is warming up to 550 DEG C of calcining 4h, is cooled to room temperature to get catalyst precursor.
Magnetic loading object: it takes Iron(III) chloride hexahydrate 3:5:7 in mass ratio that anhydrous sodium acetate, 1,6- hexamethylene diamine is added, obtains
Mixture takes mixture 3:8 in mass ratio that ethylene glycol mixing is added, is stirred 3h in 30 DEG C, then be warming up to 200 DEG C of heat preservations
10h, magnet attract, and magnet attraction is taken to wash 5 times through deionized water, dehydrated alcohol, dry to get magnetic loading object.
A kind of preparation method of nano-copper base catalyst, includes the following steps:
According to the mass fraction, 8 parts of catalyst activity bodies, 3 parts of catalyst precursors, 10 parts of magnetic loading objects, 70 parts of anhydrous second are taken
Alcohol mixing, ultrasonic disperse 30min obtain ultrasonic liquid, take ultrasonic liquid 9:6 in mass ratio that the hydroboration that concentration is 0.14mol/L is added
Sodium ethoxide solution is stirred 2h in 30 DEG C, and magnet attracts, and takes magnet attraction a through deionized water, ethanol washing, dries, i.e.,
Obtain nano-copper base catalyst.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking catalyst activity body.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking catalyst precursor.
Comparative example 3: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that magnetic loading object.
Comparative example 4: the catalyst of company of Zhengzhou City production.
Catalyst in catalyst obtained in the embodiment of the present invention and comparative example is compared into test, in air into
Row processing, result are as shown in table 1 below:
Table 1:
Catalyst of the invention carries out placing with after high-temperature process in air, and the activity of the catalyst of itself does not occur larger
Change, compared to the conventional metallic catalyst bought on the market, stability is higher, is worth promoting.
Claims (7)
1. a kind of nano-copper base catalyst, which is characterized in that including catalyst activity body, catalyst precursor, magnetic loading object；
The preparation method of the catalyst activity body, includes the following steps:
(1) take methylimidazole 1 ~ 3:10 in mass ratio ~ 20 be added methanol be stirred, obtain solution A, take cabaltous nitrate hexahydrate by
2 ~ 4:25 of mass ratio ~ 35 is added methanol and is stirred, and obtains solution B, takes solution A 4 ~ 7:2 in mass ratio ~ 4 that solution B is added, in 45 ~
50 DEG C are stirred, and stand, and centrifugation takes precipitating to wash through methanol, dry, obtain dried object, dried object is taken to keep the temperature, be cooled to room
Temperature obtains cooled material；
(2) it takes cooled material 1 ~ 4:50 in mass ratio ~ 60 that ethyl alcohol is added to be stirred, adds six water of cooled material quality 7 ~ 10%
Copper nitrate is closed, 2 ~ 3h is stirred, is centrifuged, precipitating a is taken to wash through dehydrated alcohol, it is dry, it is cold in 350 ~ 400 DEG C of calcining 1 ~ 2h
But to room temperature to get catalyst activity body.
2. nano-copper base catalyst according to claim 1, which is characterized in that the heat preservation of dried object in the step (1)
Condition are as follows: in 400 ~ 450 DEG C of 2 ~ 3h of heat preservation, control heating rate is 2 DEG C/min.
3. nano-copper base catalyst according to claim 1, which is characterized in that the preparation side of the catalyst precursor
Method includes the following steps:
It takes dicyanodiamine in quartzy Noah's ark, is passed through nitrogen protection, be warming up to 280 ~ 300 DEG C of 2 ~ 3h of heat preservation, then it is warming up to 500 ~
550 DEG C of 3 ~ 4 h of calcining, obtain calcined material, take calcined material 3 ~ 5:0.2 in mass ratio ~ 0.4:20 ~ 30 that ammonium metavanadate, deionization is added
Water, 20 ~ 30min of magnetic agitation are warming up to 70 ~ 80 DEG C and are stirred, dry, grind, and cross 80 meshes, collect sieving
Grain, is passed through nitrogen protection, and sieving particle heat-insulating, calcining are cooled to room temperature to get catalyst precursor.
4. nano-copper base catalyst according to claim 3, which is characterized in that the heat preservation of the sieving particle, calcining item
Part are as follows: in 300 ~ 350 DEG C of 1 ~ 2h of heat preservation, then be warming up to 500 ~ 550 DEG C of 3 ~ 4h of calcining.
5. nano-copper base catalyst according to claim 1, which is characterized in that the preparation method of the magnetic loading object,
Include the following steps:
It takes Iron(III) chloride hexahydrate 1 ~ 3:2 in mass ratio ~ 5:5 ~ 7 that anhydrous sodium acetate, 1,6- hexamethylene diamine is added, obtains mixture, take
Ethylene glycol mixing is added in mixture 1 ~ 3:5 in mass ratio ~ 8, is stirred in 25 ~ 30 DEG C, then be warming up to 150 ~ 200 DEG C of heat preservations,
Magnet attracts, and magnet attraction is taken to wash through deionized water, dehydrated alcohol, dry to get magnetic loading object.
6. a kind of preparation method of the nano-copper base catalyst as described in claim 1 ~ 5 any one, which is characterized in that the system
Preparation Method includes the following steps:
According to the mass fraction, 5 ~ 8 parts of catalyst activity bodies, 1 ~ 3 part of catalyst precursor, 7 ~ 10 parts of magnetic loading objects, 50 ~ 70 are taken
Part dehydrated alcohol mixing, 20 ~ 30min of ultrasonic disperse obtain ultrasonic liquid, take ultrasonic liquid 7 ~ 9:4 in mass ratio ~ 6 that sodium borohydride is added
Ethanol solution is stirred, and magnet attracts, and takes magnet attraction a through deionized water, ethanol washing, dry to get nano-copper base
Catalyst.
7. the preparation method of nano-copper base catalyst according to claim 6, which is characterized in that described to be stirred condition
Are as follows: 1 ~ 2h is stirred in 25 ~ 30 DEG C.
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