CN106423164A - CuOx catalyst, preparation method of catalyst and application of catalyst in prevention and control of environmental pollution - Google Patents
CuOx catalyst, preparation method of catalyst and application of catalyst in prevention and control of environmental pollution Download PDFInfo
- Publication number
- CN106423164A CN106423164A CN201610874791.XA CN201610874791A CN106423164A CN 106423164 A CN106423164 A CN 106423164A CN 201610874791 A CN201610874791 A CN 201610874791A CN 106423164 A CN106423164 A CN 106423164A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- cuo
- preparation
- benzenetricarboxylic acid
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 229910016553 CuOx Inorganic materials 0.000 title claims abstract description 43
- 238000003912 environmental pollution Methods 0.000 title claims abstract description 13
- 230000002265 prevention Effects 0.000 title abstract 2
- 239000000243 solution Substances 0.000 claims abstract description 76
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 35
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000013148 Cu-BTC MOF Substances 0.000 claims abstract description 32
- 239000013078 crystal Substances 0.000 claims abstract description 32
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 3
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 90
- 238000002425 crystallisation Methods 0.000 claims description 28
- 230000008025 crystallization Effects 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- VHKFFPOTSWQHPK-UHFFFAOYSA-N C(C)O.C1(=CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O Chemical compound C(C)O.C1(=CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O VHKFFPOTSWQHPK-UHFFFAOYSA-N 0.000 claims description 2
- BDSBMINFNXSZQP-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid;methanol Chemical compound OC.OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 BDSBMINFNXSZQP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- B01J35/612—
-
- B01J35/613—
-
- B01J35/617—
-
- B01J35/633—
-
- B01J35/643—
-
- B01J35/647—
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention provides a CuOx catalyst, a preparation method of the catalyst and application of the catalyst in prevention and control of environmental pollution. The preparation method disclosed by the invention comprises the following steps: 1, mixing a 1,3,5-benzene tricarbonic acid alcoholic solution and a copper nitrate solution, stirring, crystallizing and executing the next step; 2, cooling after crystallizing, washing by using a mixed solution of water and alcohol, and drying to obtain a Cu-BTC crystal; 3, roasting the Cu-BTC crystal to obtain the CuOx catalyst. The preparation method is simple, easy to operate and suitable for industrial application. The CuOx catalyst prepared by the preparation method has high dispersity, uniform octahedral structure, high specific surface area, high catalytic activity and high catalytic conversion rate of CO and is capable of preventing and controlling the environmental pollution.
Description
Technical field
The invention belongs to metallic organic framework catalysis material field is and in particular to a kind of CuOxCatalyst, its preparation method
With the application in environmental pollution.
Background technology
It is known that CO is as one of topmost air pollutants, there is the typically characteristic such as inflammable, explosive, poisonous,
The Health and Living of harm people.Discharge of chemical industry, the imperfect combustion of Fossil fuel and motor-vehicle tail-gas etc. produces
Substantial amounts of CO.Additionally, low concentration CO in CO sensor, canister respirator and enclosed system such as eliminates at the aspect is directed to CO
Purifying problem.Therefore, research and develop efficiently, high efficiency, durability, the CO catalyst of low cost there is very wide prospect.
Although noble metal catalyst has good CO low-temperature catalytic activity, such as noble metal gold (Au), platinum (Pt), palladium
(Pd), but due to high costs, it is unfavorable for commercial applications.Preparing catalyst using metallic copper (Cu) cheap and easy to get has relatively
Good commercial application prospect.But it is general for CO catalytic oxidation effect at present.Ren, Y (Ren, Y；Ma, Z；Qian, L.P；
Dai, S；He, H；Bruce, P.G.CatalLett 2009,131,146-154.) etc. mesoporous CuO prepared using hard template method urge
Agent, when 134 DEG C, CO can be only achieved 50% conversion.Huang, HW (Qu, Z.P；Yu, F.L；Zhang, X.D；Wang, Y；
Gao, J.S.Huang H.W；Zhang, L.Q；Wu, K.W；Yu, Q；Chen, Ru；Yang, H.S；Peng X.S；Ye,
Z.Z.NanoScale,2012,4,7832-7841.).Deng by regulate and control metal cation prepare nanostructured CuO catalysis
Agent, at 200 DEG C, the conversion ratio of CO reaches 90%.Wang, X (Wang, X；Liu, C；Zheng, B.J；Jiang, Y.Q；Zhang,
L；Xie, Z.X；Zheng L, S.J.Mater.Chem.A, 2013,1,282-287.) etc. Cu is synthesized by wet chemical method2O is micro-
Brilliant catalyst, at 220 DEG C, the conversion ratio of CO reaches 50.4%.Zhou, M (Zhou, M；Gao, Y.A；Wang, B.X；
Rozynek, Z；Fossum, J.O.Eur.J.Inorg.Chem.2010,5,729-34) etc. pass through carbonate assisted hydrothermal synthesis
Method goes out nanometer porous C uO, and at 160 DEG C, the conversion ratio of CO just can reach 100%.Kamsi in recent years, AE (Kasmi, A.E；
Tian, Z.Y；Vieker, H；Beyer, A；Chafik, T.Appl.Catal.B, 2016,186,10-18) etc. adopt pulse nebulization technique
Evaporation chemical vapour deposition technique builds Cu2O foil catalyst, at 150 DEG C, the conversion ratio of CO reaches 50%, when temperature is further
When being increased to 165 DEG C, the conversion ratio of CO reaches 90%.But, the catalyst activity that the above method prepares
All not good, CO conversion ratio is relatively low, limits its industrial applications.
Content of the invention
The present invention is carried out for solving the above problems, and purpose provides a kind of catalysis activity height, CO high conversion rate, simultaneously
Can be suitably used for the CuO of industrial applicationsxThe preparation method of catalyst and this catalyst and this catalyst answering in environmental pollution
With.
Present invention employs following technical scheme：
The invention provides a kind of CuOxThe preparation method of catalyst, has the feature that, comprises the steps：Step
One, 1,3,5- benzenetricarboxylic acid alcoholic solution is mixed by certain mass ratio with copper nitrate solution, after stirring 20～40min, crystallization 18
～30h, carries out next step；Step 2, cools down after crystallization, is washed with the mixed solution of water and alcohol repeatedly, is 80～120 in temperature
8～16h is dried under conditions of DEG C, obtains Cu-BTC crystal；Step 3, by Cu-BTC crystal temperature be 200～600 DEG C, anti-
Answer roasting 0.5h～3h under atmospheric condition, obtain CuOxCatalyst, wherein, CuOxIn catalyst, the value of X is 0.5～1.
The CuO providing in the present inventionxIn the preparation method of catalyst, can also have the feature that：Wherein, in step
In one, the concentration of 1,3,5- benzenetricarboxylic acid alcoholic solution is 0.1～1g/mL, the concentration 0.1～0.5g/mL of copper nitrate solution.
The CuO providing in the present inventionxIn the preparation method of catalyst, can also have the feature that：In described step
In one, 1,3,5- benzenetricarboxylic acid alcoholic solution is 1,3,5- benzenetricarboxylic acid methanol solutions or 1,3,5- benzenetricarboxylic acid ethanol solution.
The CuO providing in the present inventionxIn the preparation method of catalyst, can also have the feature that：In step one,
1,3,5- benzenetricarboxylic acid alcoholic solution is 1 with the mass ratio of copper nitrate solution:0.4～1.5.
The CuO providing in the present inventionxIn the preparation method of catalyst, can also have the feature that：In step one,
1,3,5- benzenetricarboxylic acid alcoholic solution and copper nitrate solution whipping temp are in the range of 30～40 DEG C.
The CuO providing in the present inventionxIn the preparation method of catalyst, can also have the feature that：In step 2,
Water is deionized water, and alcohol is methanol or ethanol.
The CuO providing in the present inventionxIn the preparation method of catalyst, can also have the feature that：In step 2,
Washing times are 3～5 times.
The CuO providing in the present inventionxIn the preparation method of catalyst, can also have the feature that：In step 3,
Reaction atmosphere is CO, O2、H2、N2, any one or its mixed gas in He and Ar.
The present invention also provides a kind of CuO preparing using above-mentioned preparation methodxCatalyst, has the feature that：
CuOxIn catalyst, the scope of X is 0.5～1, CuOxThe aperture of catalyst be 0.78～24nm, specific surface area be 5.1～
957.3m2/g.
Present invention also offers a kind of above-mentioned CuOxApplication in preventing and treating environmental pollution for the catalyst.
Invention effect and effect
The invention provides a kind of CuOxCatalyst, its preparation method and the application in preventing and treating environmental pollution, the present invention
Preparation method 1,3,5- benzenetricarboxylic acid alcoholic solution is mixed with copper nitrate solution, stirs, after crystallization, then washed with water and alcohol,
After drying, obtain Cu-BTC crystal；Finally obtain CuO by after Cu-BTC crystal roastingxCatalyst, preparation method is simple, easily grasps
Make it is adaptable to industrial applications.The CuO being obtained using this preparation methodxCatalyst has high dispersive, homogeneous octahedral structure
And high-specific surface area, catalysis activity height, catalyzed conversion CO high conversion rate, environmental pollution can be prevented and treated.
Brief description
Fig. 1 is CuO in the embodiment of the present invention onexThe CuO that the preparation method of catalyst is obtainedxThe X-ray diffraction of catalyst
Figure；
Fig. 2 is CuO in the embodiment of the present invention onexThe CuO that the preparation method of catalyst is obtainedxCatalyst is to N2Adsorption-desorption
Figure；
Fig. 3 is CuO in the embodiment of the present invention onexThe CuO that the preparation method of catalyst is obtainedxCatalyst graph of pore diameter distribution.
Fig. 4 is CuO in the embodiment of the present invention onexThe CuO that the preparation method of catalyst is obtainedxScanning electron microscope (SEM) photograph.
Specific embodiment
The CuO to the present invention with accompanying drawing with reference to embodimentsxCatalyst, its preparation method and preventing and treating environmental pollution in
Application be further described.
<Embodiment one>
A kind of CuOxThe preparation method of catalyst, comprises the following steps：
Step one, weighs 1.9664g 1,3,5- benzenetricarboxylic acid (H3BTC) it is dissolved in 20mL ethanol, stirring and dissolving obtains 1,
3,5- benzenetricarboxylic acid alcoholic solution；Weigh 4.48g Gerhardite Cu (NO simultaneously3)2·3H2O is dissolved in 10mL deionized water,
Stir and obtain copper nitrate solution to dissolving.
Step 2,1,3,5- benzenetricarboxylic acid alcoholic solution and copper nitrate solution are 1 in mass ratio:1.25 mixing, stirring
After 30min, load reactor under conditions of 140 DEG C crystallization 24h.
Step 3, cools down after crystallization, and the mixed solution of deionized water and ethanol washs 3 times, the baking being 100 DEG C in temperature
12h is dried in case, obtains Cu-BTC crystal.
Step 4, by Cu-BTC crystal temperature be 250 DEG C, atmosphere form (volume ratio 1%CO, 20%O2, 79%He)
Under the conditions of roasting 2h, obtain CuOx(containing CuO50%, Cu2O50%) catalyst.
Fig. 1 is CuO in the embodiment of the present invention onexThe CuO that the preparation method of catalyst is obtainedxThe X-ray diffraction of catalyst
Figure.
As shown in figure 1, CuOx(containing CuO50%, Cu2O50%) catalyst has when the angle of diffraction 2 θ=36.5 ° significantly
Diffraction maximum.
Fig. 2 is CuO in the embodiment of the present invention onexThe CuO that the preparation method of catalyst is obtainedxCatalyst is to N2Adsorption-desorption
Figure.
As shown in Fig. 2 when relative pressure is 0.05～0.8, absorbing volume and slowly increase；In relative pressure 0.8～
When 0.995, absorb volume rapid growth.
Fig. 3 is CuO in the embodiment of the present invention onexThe CuO that the preparation method of catalyst is obtainedxCatalyst graph of pore diameter distribution.
As shown in figure 3, CuOx(containing CuO50%, Cu2O50%) catalyst pore-size distribution is concentrated mainly on 1.7nm and 4nm
Place.
Fig. 4 is CuO in the embodiment of the present invention onexThe CuO that the preparation method of catalyst is obtainedxScanning electron microscope (SEM) photograph.
As shown in figure 4, after pretreated, CuOx(containing CuO50%, Cu2O50%) catalyst just still maintains
Octahedral structure.
<Embodiment two>
A kind of CuOxThe preparation method of catalyst, comprises the following steps：
Step one, weighs 1.6g 1,3,5- benzenetricarboxylic acid (H3BTC) it is dissolved in 20mL ethanol, stirring and dissolving obtains 1,3,
5- benzenetricarboxylic acid alcoholic solution；Weigh 1g Gerhardite Cu (NO simultaneously3)2·3H2O is dissolved in 10mL deionized water, stir to
Dissolving obtains copper nitrate solution.
Step 2, by 1,3,5- benzenetricarboxylic acid alcoholic solution and copper nitrate solution in mass ratio 1:0.4 mixing, stirs 20min
Afterwards, load reactor under conditions of 140 DEG C crystallization 18h.
Step 3, cools down after crystallization, and the mixed solution of deionized water and ethanol washs 4 times, the baking being 80 DEG C in temperature
8h is dried in case, obtains Cu-BTC crystal.
Step 4, by Cu-BTC crystal temperature be 200 DEG C, atmosphere composition (volume ratio be 30%O2, 70%Ar) and condition
Lower roasting 0.5h, obtains CuO catalyst.
<Embodiment three>
A kind of CuOxThe preparation method of catalyst, comprises the following steps：
Step one, weighs 10g 1,3,5- benzenetricarboxylic acid (H3BTC) it is dissolved in 20mL ethanol, stirring and dissolving obtains 1,3,5-
Benzenetricarboxylic acid alcoholic solution；Weigh 5g Gerhardite Cu (NO simultaneously3)2·3H2O is dissolved in 10mL deionized water, stirs to molten
Solution obtains copper nitrate solution.
Step 2, by 1,3,5- benzenetricarboxylic acid alcoholic solution and copper nitrate solution in mass ratio 1:1.5 mixing, stir 40min
Afterwards, load reactor under conditions of 140 DEG C crystallization 30h.
Step 3, cools down after crystallization, and the mixed solution of deionized water and ethanol washs 5 times, the baking being 120 DEG C in temperature
16h is dried in case, obtains Cu-BTC crystal.
Step 4, by Cu-BTC crystal temperature be 300 DEG C, atmosphere composition (volume ratio be 100%H2) under the conditions of roasting
3h, obtains Cu2O catalyst.
<Example IV>
A kind of CuOxThe preparation method of catalyst, comprises the following steps：
Step one, weighs 4g 1,3,5- benzenetricarboxylic acid (H3BTC) it is dissolved in 20mL ethanol, stirring and dissolving obtains 1,3,5-
Benzenetricarboxylic acid alcoholic solution；Weigh 2g Gerhardite Cu (NO simultaneously3)2·3H2O is dissolved in 10mL deionized water, stirs to molten
Solution obtains copper nitrate solution.
Step 2, by 1,3,5- benzenetricarboxylic acid alcoholic solution and copper nitrate solution in mass ratio 1:1 mixing, after stirring 30min,
Load reactor under conditions of 140 DEG C crystallization 24h.
Step 3, cools down after crystallization, and the mixed solution of deionized water and ethanol washs 4 times, the baking being 100 DEG C in temperature
12h is dried in case, obtains Cu-BTC crystal.
Step 4, by Cu-BTC crystal temperature be 250 DEG C, roasting under the conditions of atmosphere composition (volume ratio be 100%Ar)
2h, obtains CuOx(containing CuO80%, Cu2O20%) catalyst.
<Embodiment five>
A kind of CuOxThe preparation method of catalyst, comprises the following steps：
Step one, weighs 6g 1,3,5- benzenetricarboxylic acid (H3BTC) it is dissolved in 20mL ethanol, stirring and dissolving obtains 1,3,5-
Benzenetricarboxylic acid alcoholic solution；Weigh 3g Gerhardite Cu (NO simultaneously3)2·3H2O is dissolved in 10mL deionized water, stirs to molten
Solution obtains copper nitrate solution.
Step 2, by 1,3,5- benzenetricarboxylic acid alcoholic solution and copper nitrate solution in mass ratio 1:0.8 mixing, stirs 30min
Afterwards, load reactor under conditions of 140 DEG C crystallization 24h.
Step 3, cools down after crystallization, and the mixed solution of deionized water and ethanol washs 4 times, the baking being 100 DEG C in temperature
12h is dried in case, obtains Cu-BTC crystal.
Step 4, by Cu-BTC crystal temperature be 200 DEG C, atmosphere composition (volume ratio be 1%CO, 20%O2, 79%
He roasting 2h under the conditions of)), obtains CuOx(containing CuO70%, Cu2O30%) catalyst.
<Embodiment six>
A kind of CuOxThe preparation method of catalyst, comprises the following steps：
Step one, weighs 8g 1,3,5- benzenetricarboxylic acid (H3BTC) it is dissolved in 20mL ethanol, stirring and dissolving obtains 1,3,5-
Benzenetricarboxylic acid alcoholic solution；Weigh 4g Gerhardite Cu (NO simultaneously3)2·3H2O is dissolved in 10mL deionized water, stirs to molten
Solution obtains copper nitrate solution.
Step 2, by 1,3,5- benzenetricarboxylic acid alcoholic solution and copper nitrate solution in mass ratio 1:0.6 mixing, stirs 30min
Afterwards, load reactor under conditions of 140 DEG C crystallization 24h.
Step 3, cools down after crystallization, and the mixed solution of deionized water and ethanol washs 3 times, the baking being 100 DEG C in temperature
12h is dried in case, obtains Cu-BTC crystal.
Step 4, by Cu-BTC crystal temperature be 230 DEG C, atmosphere composition (volume ratio be 1%CO, 20%O2, 79%
Ar roasting 2h under the conditions of)), obtains CuOx(containing CuO60%, Cu2O40%) catalyst.
<Embodiment seven>
A kind of CuOxThe preparation method of catalyst, comprises the following steps：
Step one, weighs 1.9664g 1,3,5- benzenetricarboxylic acid (H3BTC) it is dissolved in 20mL ethanol, stirring and dissolving obtains 1,
3,5- benzenetricarboxylic acid alcoholic solution；Weigh 4.48g Gerhardite Cu (NO simultaneously3)2·3H2O is dissolved in 10mL deionized water,
Stir and obtain copper nitrate solution to dissolving.
Step 2, by 1,3,5- benzenetricarboxylic acid alcoholic solution and copper nitrate solution in mass ratio 1:1.25 mixing, stir 30min
Afterwards, load reactor under conditions of 140 DEG C crystallization 24h.
Step 3, cools down after crystallization, and the mixed solution of deionized water and ethanol washs 4 times, the baking being 100 DEG C in temperature
12h is dried in case, obtains Cu-BTC crystal.
Step 4, by Cu-BTC crystal temperature be 400 DEG C, atmosphere form (100%N2) under the conditions of roasting 2h, obtain
CuOx(containing CuO40%, Cu2O60%) catalyst.
<Embodiment eight>
A kind of CuOxThe preparation method of catalyst, comprises the following steps：
Step one, weighs 1.9664g 1,3,5- benzenetricarboxylic acid (H3BTC) it is dissolved in 20mL ethanol, stirring and dissolving obtains 1,
3,5- benzenetricarboxylic acid alcoholic solution；Weigh 4.48g Gerhardite Cu (NO simultaneously3)2·3H2O is dissolved in 10mL deionized water,
Stir and obtain copper nitrate solution to dissolving.
Step 2,1,3,5- benzenetricarboxylic acid alcoholic solution and copper nitrate solution are compared 1 by certain mass:1.25 mixing, stirring
After 30min, load reactor under conditions of 140 DEG C crystallization 24h.
Step 3, cools down after crystallization, and the mixed solution of deionized water and ethanol washs 4 times, the baking being 100 DEG C in temperature
12h is dried in case, obtains Cu-BTC crystal.
Step 4, by Cu-BTC crystal temperature be 600 DEG C, atmosphere composition (100%He) under the conditions of roasting 2h, obtain
CuOx(containing CuO30%, Cu2O70%) catalyst.
<Embodiment nine>
A kind of CuOxThe preparation method of catalyst, comprises the following steps：
Step one, weighs 1.9664g 1,3,5- benzenetricarboxylic acid (H3BTC) it is dissolved in 20mL ethanol, stirring and dissolving obtains 1,
3,5- benzenetricarboxylic acid alcoholic solution；Weigh 4.48g Gerhardite Cu (NO simultaneously3)2·3H2O is dissolved in 10mL deionized water,
Stir and obtain copper nitrate solution to dissolving.
Step 2, by 1,3,5- benzenetricarboxylic acid alcoholic solution and copper nitrate solution in mass ratio 1:1.25 mixing, stir 30min
Afterwards, load reactor under conditions of 140 DEG C crystallization 24h.
Step 3, cools down after crystallization, and the mixed solution of deionized water and ethanol washs 4 times, the baking being 100 DEG C in temperature
12h is dried in case, obtains Cu-BTC crystal.
Step 4, by Cu-BTC crystal temperature be 500 DEG C, atmosphere composition (volume ratio be 1%CO, 20%O2, 79%
He roasting 0.5h under the conditions of)), obtains CuOx(containing CuO20%, Cu2O80%) catalyst.
<Embodiment ten>
A kind of CuOxThe preparation method of catalyst, comprises the following steps：
Step one, weighs 1.9664g 1,3,5- benzenetricarboxylic acid (H3BTC) it is dissolved in 20mL ethanol, stirring and dissolving obtains 1,
3,5- benzenetricarboxylic acid alcoholic solution；Weigh 4.48g Gerhardite Cu (NO simultaneously3)2·3H2O is dissolved in 10mL deionized water,
Stir and obtain copper nitrate solution to dissolving.
Step 2, by 1,3,5- benzenetricarboxylic acid alcoholic solution and copper nitrate solution in mass ratio 1:1 mixing, after stirring 30min,
Load reactor under conditions of 140 DEG C crystallization 24h.
Step 3, cools down after crystallization, and the mixed solution of deionized water and ethanol washs 4 times, the baking being 100 DEG C in temperature
12h is dried in case, obtains Cu-BTC crystal.
Step 4, by Cu-BTC crystal temperature be 250 DEG C, atmosphere composition (volume ratio be 1%CO, 20%O2, 79%
He roasting 1h under the conditions of)), obtains CuOx(containing CuO10%, Cu2O90%) catalyst.
<Embodiment 11>
A kind of CuOxThe preparation method of catalyst, comprises the following steps：
Step one, weighs 1.9664g 1,3,5- benzenetricarboxylic acid (H3BTC) it is dissolved in 20mL ethanol, stirring and dissolving obtains 1,
3,5- benzenetricarboxylic acid alcoholic solution；Weigh 4.48g Gerhardite Cu (NO simultaneously3)2·3H2O is dissolved in 10mL deionized water,
Stir and obtain copper nitrate solution to dissolving.
Step 2, by 1,3,5- benzenetricarboxylic acid alcoholic solution and copper nitrate solution in mass ratio 1:1 mixing, after stirring 30min,
Load reactor under conditions of 140 DEG C crystallization 24h.
Step 3, cools down after crystallization, and the mixed solution of deionized water and ethanol washs 4 times, the baking being 100 DEG C in temperature
12h is dried in case, obtains Cu-BTC crystal.
Step 4, by Cu-BTC crystal temperature be 250 DEG C, atmosphere composition (volume ratio be 1%CO, 20%O2, 79%N2)
Under the conditions of roasting 1.5h, obtain CuOx(containing CuO15%, Cu2O85%) catalyst.
Catalyst activity evaluation experimental
The CuO that one to embodiment 11 prepares will be implementedxCatalyst respectively fixed bed continuously flow differential reaction
Reacted in device, the internal diameter of differential reactor is the glass U-tube of 4mm, the loadings of catalyst are 100mg.
Part I：The constituent of unstripped gas is 1%CO, 20%O for volume ratio2, 79%He, gas flow rate is
30ml/min, after reaction 20min in continuous flowing differential reactor, in product gas, CO is through being furnished with thermal conductivity cell detector GC-
2060 gas chromatograph on-line analyses, finally obtain CO conversion ratio, and CO conversion ratio represents CuOxThe reactivity of catalyst；
Part II：The Ar of 2ml/min, by being placed in the saturator of the toluene in cold-trap, carries toluene and 33m1/min's
30%O2After the Ar mixing of/Ar and 15ml/min, after reaction 20min in continuous flowing differential reactor, first in product gas
Benzene, through being furnished with hydrogen flame detector GC-2060 gas chromatograph on-line analyses, finally obtains toluene conversion, toluene conversion is
Represent CuOxThe reactivity of catalyst；And mixed toluene concentration is maintained at 1000ppm, air speed is 37500h-1.
Activity rating finally gives table 1 below, 2 results, as shown in table 1,2：
Table 1 CuOxCatalyst performance index
Table 2 CuOxThe catalytic performance of catalyst
Embodiment effect and effect
Embodiment one provides a kind of CuO to embodiment 11xCatalyst, its preparation method and preventing and treating environmental pollution in
Application, 1,3,5- benzenetricarboxylic acid alcoholic solution is mixed with copper nitrate solution, stirs by the preparation method of the present invention, after crystallization, then
Washed with water and alcohol, after being dried, obtain Cu-BTC crystal；Finally obtain CuO by after Cu-BTC crystal roastingxCatalyst, preparation
Method is simple, easy to operate it is adaptable to industrial applications.The CuO being obtained using this preparation methodxCatalyst has high dispersive, all
One octahedral structure and high-specific surface area, catalysis activity is high, and catalyzed conversion CO high conversion rate can prevent and treat environmental pollution.
Above example is only the basic explanation under present inventive concept, does not limit the invention.And according to the present invention
Any equivalent transformation of being made of technical scheme, belong to protection scope of the present invention.
Claims (10)
1. a kind of CuOxThe preparation method of catalyst is it is characterised in that comprise the steps：
Step one, 1,3,5- benzenetricarboxylic acid alcoholic solution is mixed by certain mass ratio with copper nitrate solution, stirs 20～40min
Afterwards, crystallization 18～30h, carries out next step；
Step 2, cools down after crystallization, is washed with the mixed solution of water and alcohol repeatedly, dry under conditions of temperature is 80～120 DEG C
Dry 8～16h, obtains Cu-BTC crystal；
Step 3, by described Cu-BTC crystal temperature be 200～600 DEG C, roasting 0.5h～3h under the conditions of reaction atmosphere, obtain
Described CuOxCatalyst,
Wherein, described CuOxIn catalyst, the value of X is 0.5～1.
2. CuO according to claim 1xThe preparation method of catalyst it is characterised in that：
Wherein, in described step one, the concentration of described 1,3,5- benzenetricarboxylic acid alcoholic solutions is 0.1～1g/mL, described copper nitrate
Concentration 0.1～the 0.5g/mL of solution.
3. CuO according to claim 1xThe preparation method of catalyst it is characterised in that：
Wherein, in described step one, described 1,3,5- benzenetricarboxylic acid alcoholic solutions are 1,3,5- benzenetricarboxylic acid methanol solutions or 1,
3,5- benzenetricarboxylic acid ethanol solution.
4. CuO according to claim 1xThe preparation method of catalyst it is characterised in that：
Wherein, in described step one, described 1,3,5- benzenetricarboxylic acid alcoholic solutions are 1 with the mass ratio of copper nitrate solution：0.4～
1.5.
5. CuO according to claim 1xThe preparation method of catalyst it is characterised in that：
Wherein, in described step one, described 1,3,5- benzenetricarboxylic acid alcoholic solutions and described copper nitrate solution whipping temp are 30
In the range of～40 DEG C.
6. CuO according to claim 1xThe preparation method of catalyst it is characterised in that：
Wherein, in described step 2, described water is deionized water, and described alcohol is methanol or ethanol.
7. CuO according to claim 1xThe preparation method of catalyst it is characterised in that：
Wherein, in described step 2, washing times are 3～5 times.
8. CuO according to claim 1xThe preparation method of catalyst it is characterised in that：
Wherein, in described step 3, described reaction atmosphere is CO, O2、H2、N2, any one or its mixing in He and Ar
Gas.
9. the CuO described in a kind of any one as claim 1～8xThe CuO that the preparation method of catalyst preparesxCatalysis
Agent it is characterised in that：
Described CuOxThe aperture of catalyst is 0.78～24nm, and specific surface area is 5.1～957.3m2/g.
10. a kind of CuO as described in claim 9xApplication in preventing and treating environmental pollution for the catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610874791.XA CN106423164A (en) | 2016-09-30 | 2016-09-30 | CuOx catalyst, preparation method of catalyst and application of catalyst in prevention and control of environmental pollution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610874791.XA CN106423164A (en) | 2016-09-30 | 2016-09-30 | CuOx catalyst, preparation method of catalyst and application of catalyst in prevention and control of environmental pollution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106423164A true CN106423164A (en) | 2017-02-22 |
Family
ID=58171682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610874791.XA Pending CN106423164A (en) | 2016-09-30 | 2016-09-30 | CuOx catalyst, preparation method of catalyst and application of catalyst in prevention and control of environmental pollution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106423164A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047027A (en) * | 2017-12-21 | 2018-05-18 | 万华化学集团股份有限公司 | A kind of preparation method of the system and method for preparing isononanoic acid and metal organic framework catalyst |
| CN108607565A (en) * | 2018-04-19 | 2018-10-02 | 上海理工大学 | A kind of CuO/CeO2Catalyst and its preparation method and application |
| CN109659571A (en) * | 2019-01-29 | 2019-04-19 | 东华大学 | A kind of carbon dioxide electrochemical reduction catalyst and the application in zero distance reactor |
| CN112958089A (en) * | 2021-02-08 | 2021-06-15 | 哈尔滨工业大学 | Preparation method of copper oxide catalyst for catalyzing persulfate to degrade pollutants in water |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172105A (en) * | 2013-04-09 | 2013-06-26 | 江西师范大学 | Method for preparing CuO multilevel nanometer structure based on metal organic framework material Cu3(BTC)2.nH2O |
| CN105664944A (en) * | 2016-02-19 | 2016-06-15 | 中国环境科学研究院 | Cu catalyst based on metal organic framework, preparation method and application |
-
2016
- 2016-09-30 CN CN201610874791.XA patent/CN106423164A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172105A (en) * | 2013-04-09 | 2013-06-26 | 江西师范大学 | Method for preparing CuO multilevel nanometer structure based on metal organic framework material Cu3(BTC)2.nH2O |
| CN105664944A (en) * | 2016-02-19 | 2016-06-15 | 中国环境科学研究院 | Cu catalyst based on metal organic framework, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| QING MIN WANG等: "Metallo-organic molecular sieve for gas separation and purification", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| 张晓东等: "基于金属有机骨架材料Cu-BTC 前驱体的纳米材料结构的调控及其性能研究", 《第九界全国环境催化与环境材料学术会议——助力两型社会快速发展的环境催化与环境催化与环境材料会议论文集》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047027A (en) * | 2017-12-21 | 2018-05-18 | 万华化学集团股份有限公司 | A kind of preparation method of the system and method for preparing isononanoic acid and metal organic framework catalyst |
| CN108607565A (en) * | 2018-04-19 | 2018-10-02 | 上海理工大学 | A kind of CuO/CeO2Catalyst and its preparation method and application |
| CN108607565B (en) * | 2018-04-19 | 2021-02-26 | 上海理工大学 | CuO/CeO2Catalyst, preparation method and application thereof |
| CN109659571A (en) * | 2019-01-29 | 2019-04-19 | 东华大学 | A kind of carbon dioxide electrochemical reduction catalyst and the application in zero distance reactor |
| CN109659571B (en) * | 2019-01-29 | 2022-02-01 | 东华大学 | Carbon dioxide electrochemical reduction catalyst and application thereof in zero-distance reactor |
| CN112958089A (en) * | 2021-02-08 | 2021-06-15 | 哈尔滨工业大学 | Preparation method of copper oxide catalyst for catalyzing persulfate to degrade pollutants in water |
| CN112958089B (en) * | 2021-02-08 | 2023-09-01 | 哈尔滨工业大学 | Preparation method of copper oxide catalyst for catalyzing persulfate to degrade pollutants in water |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Performance of modified La x Sr1–x MnO3 perovskite catalysts for NH3 oxidation: TPD, DFT, and kinetic studies | |
| Li et al. | Photo-assisted selective catalytic reduction of NO by Z-scheme natural clay based photocatalyst: Insight into the effect of graphene coupling | |
| Zeng et al. | Synergistic effect of tunable oxygen-vacancy defects and graphene on accelerating the photothermal degradation of methanol over Co3O4/rGO nanocomposites | |
| Ding et al. | Efficient visible light driven photocatalytic removal of NO with aerosol flow synthesized B, N-codoped TiO2 hollow spheres | |
| Liu et al. | Insight into the mechanism of photocatalytic degradation of gaseous o-dichlorobenzene over flower-type V 2 O 5 hollow spheres | |
| CN106423164A (en) | CuOx catalyst, preparation method of catalyst and application of catalyst in prevention and control of environmental pollution | |
| Li et al. | Construction of LaFe1− xMnxO3/attapulgite nanocomposite for photo-SCR of NOx at low temperature | |
| Tarjomannejad et al. | Catalytic Oxidation of CO Over LaMn 1− x B x O 3 (B= Cu, Fe) Perovskite-type Oxides | |
| Huang et al. | Fluorescent light enhanced graphitic carbon nitride/ceria with ultralow-content platinum catalyst for oxidative decomposition of formaldehyde at ambient temperature | |
| CN109201048A (en) | A kind of monatomic catalyst and preparation method thereof | |
| Zhao et al. | Multi-phase coexisting metal oxide derived by MOFs for the CO-SCR reaction at low temperature and in situ DRIFTS study on reaction mechanism | |
| Zhang et al. | Oxygen activation of noble-metal-free g-C3N4/α-Ni (OH) 2 to control the toxic byproduct of photocatalytic nitric oxide removal | |
| Cai et al. | Highly selective catalytic reduction of NO via SO 2/H 2 O-tolerant spinel catalysts at low temperature | |
| CN102068991B (en) | High dispersed loaded nano-metal Ni catalyst and preparation method thereof | |
| CN114618589A (en) | Preparation method and application of ozone degradation catalyst based on iron-based organic framework | |
| Karakas et al. | Room Temperature Photocatalytic Oxidation of Carbon Monoxide Over Pd/TiO 2–SiO 2 Catalysts | |
| Yuan et al. | Composite nanofiber membrane embedded TiO2/diatomite catalyst for highly efficient mineralization of formaldehyde | |
| Wang et al. | Aerosol processing of mesoporous silica supported bimetallic catalysts for low temperature acetone oxidation | |
| Huang et al. | Photocatalytic oxidation of nitrogen oxides over {001} TiO 2: the influence of F− ions | |
| CN109967076B (en) | Supported catalyst and preparation method thereof | |
| Zhang et al. | NiCo-LDH@ MnO2 nanocages as advanced catalysts for efficient formaldehyde elimination | |
| Wang et al. | Influence of LaCoO3 perovskite oxides prepared by different method on the catalytic combustion of ethyl acetate in the presence of NO | |
| Zhou et al. | Cryptomelane nanowires for highly selective self-heating photothermal synergistic catalytic oxidation of gaseous ammonia | |
| Wang et al. | Selective catalytic reduction of NO by CO over MOF-based CuOx@ ZIF-67 catalysts and reaction mechanism | |
| Sun et al. | Boosting acetone oxidation performance over mesocrystal MxCe1-xO2 (M= Ni, Cu, Zn) solid solution within hollow spheres by tailoring transition-metal cations |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170222 |