CN108993472A - A kind of titanium dioxide carbon nanotube composite carried catalyst and preparation and application - Google Patents
A kind of titanium dioxide carbon nanotube composite carried catalyst and preparation and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 66
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 title claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 230000003197 catalytic effect Effects 0.000 claims abstract description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 11
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- 239000011149 active material Substances 0.000 claims abstract description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 239000008367 deionised water Substances 0.000 claims description 43
- 229910021641 deionized water Inorganic materials 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 238000007254 oxidation reaction Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 23
- 229960000583 acetic acid Drugs 0.000 claims description 22
- 238000003760 magnetic stirring Methods 0.000 claims description 22
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- 239000012362 glacial acetic acid Substances 0.000 claims description 14
- 239000002351 wastewater Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 230000020477 pH reduction Effects 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims 1
- 229940088710 antibiotic agent Drugs 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000010306 acid treatment Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 description 41
- 229960001699 ofloxacin Drugs 0.000 description 41
- 230000003647 oxidation Effects 0.000 description 26
- 239000002253 acid Substances 0.000 description 23
- 229910002651 NO3 Inorganic materials 0.000 description 21
- 238000002474 experimental method Methods 0.000 description 20
- 238000012545 processing Methods 0.000 description 20
- 238000002955 isolation Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 10
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000010815 organic waste Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000011953 bioanalysis Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Abstract
The present invention relates to a kind of methods that sol-gel method prepares titanium dioxide, carbon nanotube composite carried catalyst.The present invention is using butyl titanate as titania support titanium source, using the carbon nanotube of sulfuric acid or nitric acid treatment as another component of complex carrier, with CeO2、Co3O4、Bi2O3, one or both of NiO be active material, efficient persulfate catalyst is prepared by the hydrolysis gel of butyl titanate.The features such as this preparation method has preparation method simple, and stability is good, active component good dispersion, low-temperature catalytic activity height and good pH universality.
Description
Technical field
The present invention relates to the method and its application that a kind of composite material carrier prepares persulfate catalyst, have catalysis
Active high, stability is good, catalytic condition requires low feature, is suitable for industrial degradation of organic waste water.Belong to water treatment technology and
Field of environment engineering.
Technical background
Water is important natural resources for the survival of mankind, in recent years, with the rapid development of industry, in production and life
The waste and pollution of water resource greatly promote, and wherein organic wastewater is very harmful one of several in industrial wastewater.Due to work
Mostly containing phenolic comp ' ds pollution, pesticide, dyestuff, Polychlorinated biphenyls etc. in industry organic wastewater, so most of industrial organic waste waters have
The features such as bio-toxicity is big, it is biodegradable, carcinogenic to be difficult to, teratogenesis.
Currently, the technology of processing organic wastewater has physical method, chemical method, bioanalysis.Wherein physical method is mainly for suspension
Type pollutant is separated, but can not change the chemical property of pollutant, be easy to cause secondary pollution.Bioanalysis utilizes micro- life
The own metabolism of object acts on degradable organic pollutant.Since organic pollutant has high bio-toxicity, bioanalysis degradation organic waste
Water effect is poor.The main method of degradation of organic waste water is chemical oxidization method at present.Wherein advanced oxidation processes due to it efficiently, it is fast
Speed feature and be widely applied.
TiO2Have many advantages, such as that low in cost, without secondary pollution, chemical property is stablized.TiO2Have emphatically in photocatalysis field
The status wanted is often used TiO in traditional Fenton system2Carrier is done to achieve the purpose that accelerate reaction rate.The present invention
By TiO2Carrier is used for persulfate oxidation system, improves the dispersibility of active component in the catalyst.
Carbon nanotube is a kind of new material quickly grown in recent years, and with large specific surface area, intensity is high, chemically
Matter stablize, the good characteristics such as high-fire resistance, at the same its in environment heavy metal and organic pollutant have very strong suction
Attached ability.Due to performances such as the excellent mechanics of carbon nanotube, calorifics, it is prepared as catalyst carrier, is promoting reaction rate
While, it can greatly promote the stability of catalyst.Although carbon nanotube has many good characteristics, since itself is managed
The limitation for changing property causes its dispersibility in system very poor, it is difficult to directly apply to preparation catalyst carrier.It is answered in engineering
The processing method that modification is a kind of carbon nano-tube modification is carried out with tube wall of the oxidizing acid to carbon nanotube, oxidizing acid can be
Carboxyl is introduced on the tube wall of carbon nanotube, the groups such as hydroxyl improve the hydrophily of carbon nanotube, increase its dispersion in water
Property.The modified carbon nanotube of acid is prepared as catalyst carrier, it is dispersed by significant increase.
In recent years, it is based on SO4 -High-level oxidation technology be rapidly developed in terms of the processing of organic wastewater.Classical
In high-level oxidation technology, OH has the shortcomings that there are the time is short insufficient with oxidability.Compared to OH, SO4 -With energy of oxidation
The advantage that power is strong, the service life is long, pH application range is wide.The research and application to persulfate high-level oxidation technology domestic at present is still
Few, persulfate consumes energy there are still activation method high problem in actual application.Therefore finding can be in low catalysis item
The method for preparing catalyst that persulfate is efficiently activated under part is key problem in technology.The present invention provides it is a kind of can be under cryogenic
The method for preparing catalyst of efficient catalytic over cure acid group activation, it would be desirable in the advanced oxidation processes degradation of industrial organic waste water
To promotion and application.
Summary of the invention
The present invention provides the method and its application that a kind of composite material carrier prepares efficient persulfate catalyst, with acidification
Modified carbon nanotube and titanium dioxide is complex carrier, with CeO2、Co3O4、Bi2O3, one or both of NiO be active matter
Matter makes a kind of efficient persulfate catalyst.SO can be generated by activation over cure acid group in persulfate oxidation reaction4 -,
The degradation rate for improving organic matter removes organic wastewater efficiently, rapidly.
The present invention also provides the preparation method of above-mentioned catalyst, a kind of titanium dioxide, the catalysis of carbon nanotube complex carrier
The preparation method of agent, comprising the following steps:
Step 1, carbon nanotube is dipped to and is totally submerged with 50-70% (most preferably 55-65%) concentrated nitric acid or the concentrated sulfuric acid,
It is acidified 20-30h (most preferably 22-28h).After deionized water is repeatedly washed, the carbon nanotube for floating on deionized water surface is gone
It removes, takes lower sediment carbon nanotube to filter, drying；
Step 2, b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, be placed in magnetic stirring apparatus with
The revolving speed of 100-200rpm (most preferably 125-180rpm) stirs；
Step 3, one or both of cerous nitrate, cobalt nitrate, bismuth nitrate, nickel nitrate are dissolved in d mol deionized water
Middle formation solution B adjusts pH with glacial acetic acid；
Step 4, under conditions of magnetic stirring apparatus is stirred continuously, by solution B with 10-20mL/min (most preferably 12-
Speed 18mL/min) is slowly dropped to solution A and forms AB mixed solution；
Step 5, stop stirring, carbon nanotube after a g acidification is put into AB mixed liquor, 60-100kHz is (most preferably
Ultrasonic disperse under 70-90kHz) is until it becomes gel；
Step 6, after gel is almost dry, it is put into tubular type kiln roasting, it is compound to obtain titanium dioxide, carbon nanotube
Carrier high-efficiency catalyst.
With CeO2、Co3O4、Bi2O3, one or both of NiO be active material, its activity component load quantity in terms of metal
For 1.0~5.0wt.%.
C/b is 20-30 in the step 2.
In the step 3 with d/b in step 2 be 5-10.
It is 3-4 that glacial acetic acid, which adjusts mixed solution pH value, in the step 3.
A/ (79.87b) is 0.5-2.5 (titania molecule amount: 79.87g/mol) in the step 2 and step 5.
Maturing temperature is 500-700 DEG C of roasting 240-300min in the step 6.
The intermittent reaction condition of the catalyst treatment organic wastewater are as follows: normal pressure, initial pH on wastewater 3-11, reaction temperature
It is 20-60 DEG C, PMS (potassium hydrogen persulfate) dosage 6-8g/L, catalyst amounts 0.05-0.5g/L, water-bath constant temperature oscillator
Revolving speed 100-150r/min.
Catalytic wet oxidation catalyst of the invention has the advantage that
1. catalyst has very high low-temperature catalytic activity for the activation of over cure acid group；
2. catalyst is with good stability during oxidative degradation organic wastewater；
3. the lower production costs of catalyst；
4. catalyst has good pH universality.
Detailed description of the invention
Fig. 1 is catalyst relational graph, catalysis oxidation Ofloxacin degradation rate and time chart in embodiment 1.
Fig. 2 is titanium dioxide, carbon nanotube complex carrier effective catalyst successive reaction life assessment figure in embodiment 1.
Specific embodiment
Efficient persulfate catalyst prepared by the present invention, can efficiently and rapidly oxidized organic wastewater, improve organic
Object removal rate.
It is described in detail below in conjunction with embodiment and attached drawing.
Embodiment 1:
1. taking carbon nanotube, it is totally submerged with 60% concentrated nitric acid, nitrifies 30h.Deionized water 5
After secondary washing, the carbon nanotube for floating on deionized water surface is removed, lower sediment carbon nanotube is taken to filter, dry
It is dry.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 100rpm
Revolving speed stirring.By Co (NO3)2·6H2O is dissolved in d mol deionized water and forms solution B, and adjusting pH value with glacial acetic acid is 3.
(wherein: b/c=25, c/d=5)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g nitre is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 80kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 500 DEG C of roasting 270min, its active component Co in terms of metal3O4Load capacity is
2.0wt.%.(wherein: a/ (79.87b)=0.5)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 6g/L, and water-bath constant temperature oscillator is anti-with 40 DEG C of water-baths of revolving speed of 150r/min
After answering 75min, Ofloxacin conversion ratio is that 99%, TOC removal rate is 77%.
Embodiment 2:
1. taking carbon nanotube, it is totally submerged with 50% concentrated sulfuric acid, acidification is for 24 hours.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 100rpm
Revolving speed stirring.By Bi (NO3)3·5H2O is dissolved in d mol deionized water and forms solution B, and adjusting pH value with glacial acetic acid is 3.
(wherein: b/c=30, c/d=8)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g sulphur is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 60kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 600 DEG C of roasting 270min, its active component Bi in terms of metal2O3Load capacity is
4.0wt.%.(wherein: a/ (79.87b)=1)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 120min, Ofloxacin conversion ratio is that 95%, TOC removal rate is 72%.
Embodiment 3:
1. taking carbon nanotube, it is totally submerged with 65% concentrated nitric acid, acidification is for 24 hours.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 200rpm
Revolving speed stirring.By Co (NO3)2·6H2O and Ni (NO3)2·6H2O is dissolved in d mol deionized water and forms solution B, with ice vinegar
Acid for adjusting pH value is 3.(wherein: b/c=25, c/d=5)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g nitre is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 80kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 500 DEG C of roasting 300min, its active component NiO load capacity is in terms of metal
2.0wt.%, Co3O4Load capacity is 2.0wt.%.(wherein: a/ (79.87b)=0.5)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 90min, Ofloxacin conversion ratio is that 96%, TOC removal rate is 74%.
Embodiment 4:
1. taking carbon nanotube, it is totally submerged with 50% concentrated nitric acid, is acidified 30h.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 200rpm
Revolving speed stirring.By Ce (NO3)3·6H2O is dissolved in d mol deionized water and forms solution B, and adjusting pH value with glacial acetic acid is 4.
(wherein: b/c=20, c/d=7)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g nitre is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 100kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 700 DEG C of roasting 270min, its active component CeO in terms of metal2Load capacity is
5.0wt.%.(wherein: a/ (79.87b)=2)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 6g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 100min, Ofloxacin conversion ratio is that 100%, TOC removal rate is 88%.
Embodiment 5:
1. taking carbon nanotube, it is totally submerged with 50% concentrated sulfuric acid, is acidified 20h.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 180rpm
Revolving speed stirring.By Ce (NO3)3·6H2O and Co (NO3)2·6H2O is dissolved in d mol deionized water and forms solution B, with ice vinegar
Acid for adjusting pH value is 4.(wherein: b/c=23, c/d=6)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g sulphur is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 90kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 700 DEG C of roasting 270min, its activity component load quantity CeO in terms of metal2For
1.0wt.%, Co3O4For 2.0wt.%.(wherein: a/ (79.87b)=1)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 90min, Ofloxacin conversion ratio is that 99%, TOC removal rate is 76%.
Embodiment 6:
1. taking carbon nanotube, it is totally submerged with 65% concentrated nitric acid, is acidified 30h.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 200rpm
Revolving speed stirring.By Co (NO3)2·6H2O and Bi (NO3)3·5H2O is dissolved in d mol deionized water and forms solution B, with ice vinegar
Acid for adjusting pH value is 3.(wherein: b/c=25, c/d=5)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g nitre is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 80kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 500 DEG C of roasting 300min, its active component Bi in terms of metal2O3Load capacity is
1.0wt.%, Co3O4Load capacity is 2.0wt.%.(wherein: a/ (79.87b)=2.5)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 90min, Ofloxacin conversion ratio is that 97%, TOC removal rate is 76%.
Embodiment 7:
1. taking carbon nanotube, it is totally submerged with 65% concentrated sulfuric acid, is acidified 28h.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 120rpm
Revolving speed stirring.By Bi (NO3)3·5H2O and Ni (NO3)2·6H2O is dissolved in d mol deionized water and forms solution B, with ice vinegar
Acid for adjusting pH value is 3.(wherein: b/c=27, c/d=8)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g sulphur is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 80kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 550 DEG C of roasting 270min, its active component NiO load capacity is in terms of metal
2.0wt.%, Bi2O3Load capacity is 2.0wt.%.(wherein: a/ (79.87b)=1.5)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 120min, Ofloxacin conversion ratio is that 98%, TOC removal rate is 78%.
Embodiment 8:
1. taking carbon nanotube, it is totally submerged with 70% concentrated sulfuric acid, is acidified 26h.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 150rpm
Revolving speed stirring.By Co (NO3)2·6H2O and Ni (NO3)2·6H2O is dissolved in d mol deionized water and forms solution B, with ice vinegar
Acid for adjusting pH value is 4.(wherein: b/c=30, c/d=5)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g sulphur is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 100kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 650 DEG C of roasting 260min, its active component NiO load capacity is in terms of metal
1.0wt.%, Co3O4Load capacity is 1.0wt.%.(wherein: a/ (79.87b)=0.5)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 100min, Ofloxacin conversion ratio is that 95%, TOC removal rate is 72%.
Embodiment 9:
1. taking carbon nanotube, it is totally submerged with 60% concentrated nitric acid, is acidified 22h.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 170rpm
Revolving speed stirring.By Ni (NO3)2·6H2O is dissolved in d mol deionized water and forms solution B, and adjusting pH value with glacial acetic acid is 3.
(wherein: b/c=22, c/d=8)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g nitre is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 60kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 650 DEG C of roasting 300min, its active component NiO load capacity is in terms of metal
3.0wt.%.(wherein: a/ (79.87b)=1)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 90min, Ofloxacin conversion ratio is that 94%, TOC removal rate is 74%.
Embodiment 10:
1. taking carbon nanotube, it is totally submerged with 50% concentrated nitric acid, is acidified 20h.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 200rpm
Revolving speed stirring.By Ni (NO3)2·6H2O and Ce (NO3)3·6H2O is dissolved in d mol deionized water and forms solution B, with ice vinegar
Acid for adjusting pH value is 3.(wherein: b/c=25, c/d=5)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g nitre is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 90kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 500 DEG C of roasting 300min, its active component NiO load capacity is in terms of metal
1.0wt.%, CeO2Load capacity is 2.0wt.%.(wherein: a/ (79.87b)=0.5)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 90min, Ofloxacin conversion ratio is that 93%, TOC removal rate is 75%.
Comparative example 1:
1. using titania powder as carrier incipient impregnation Co (NO3)2·6H2O and Ce (NO3)3·6H2O solution,
300min is roasted at 700 DEG C, obtains TiO 2 carrying body catalyst, its active component CeO in terms of metal2Load capacity is
2.0wt.%, Co3O4For 2.0wt.%.
2. catalytic oxidation experiment condition: catalyst amounts 0.5g/L, Ofloxacin initial concentration are 100mg/
L, potassium hydrogen persulfate dosage is 8g/L, after water-bath constant temperature oscillator is with 50 DEG C of water-bath 120min of revolving speed of 150r/min,
Ofloxacin conversion ratio is that 56%, TOC removal rate is 48%.Comparative example 2:
1. using carbon nanotube as carrier incipient impregnation Ce (NO3)3·6H2O solution roasts 280min at 600 DEG C, obtains
To carbon nanotube carrier catalyst, its active component CeO in terms of metal2Load capacity is 3.0wt.%.
2. catalytic oxidation experiment condition: catalyst amounts 0.5g/L, Ofloxacin initial concentration are 100mg/
L, potassium hydrogen persulfate dosage is 6g/L, after water-bath constant temperature oscillator is with 50 DEG C of water-bath 120min of revolving speed of 150r/min,
Ofloxacin conversion ratio is that 68%, TOC removal rate is 57%.Comparative example 3:
1. taking carbon nanotube, it is totally submerged with 50% concentrated sulfuric acid, is acidified 20h.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 150rpm
Revolving speed stirring.By Co (NO3)2·6H2O is dissolved in d mol deionized water and forms solution B, and adjusting pH value with glacial acetic acid is 4.
(wherein: b/c=25, c/d=2)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g sulphur is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 80kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 500 DEG C of roasting 240min, its active component Co in terms of metal3O4For
2.0wt.%.(wherein: a/ (79.87b)=2)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 6g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 100min, Ofloxacin conversion ratio is that 68%, TOC removal rate is 58%.
Comparative example 4:
1. taking carbon nanotube, it is totally submerged with 50% nitric acid, acidification is for 24 hours.It after deionized water is repeatedly washed, filters, dry
It is dry.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 160rpm
Revolving speed stirring.By Co (NO3)2·6H2O and Ce (NO3)3·6H2O is dissolved in d mol deionized water and forms solution B.(wherein:
B/c=24, c/d=7)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g nitre is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 60kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 500 DEG C of roasting 240min, its active component Co in terms of metal3O4For
1.0wt.%, CeO2For 2.0wt.%.(wherein: a/ (79.87b)=0.1)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 6g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 100min, Ofloxacin conversion ratio is that 65%, TOC removal rate is 59%.
Comparative example 5:
1. taking carbon nanotube, it is totally submerged with 50% sulfuric acid, is acidified 20h.It after deionized water is repeatedly washed, filters, dry
It is dry.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 200rpm
Revolving speed stirring.By Bi (NO3)3·5H2O and Ce (NO3)3·6H2O is dissolved in d mol deionized water and forms solution B.(wherein:
B/c=10, c/d=7)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g sulphur is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 70kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 600 DEG C of roasting 240min, its active component Bi in terms of metal2O3For
2.0wt.%, CeO2For 1.0wt.%.(wherein: a/ (79.87b)=0.5)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 6g/L, and water-bath constant temperature oscillator is anti-with 40 DEG C of water-baths of revolving speed of 150r/min
After answering 120min, Ofloxacin conversion ratio is that 70%, TOC removal rate is 62%.
Comparative example 6:
1. taking carbon nanotube, it is totally submerged with 50% concentrated sulfuric acid, acidification is for 24 hours.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 180rpm
Revolving speed stirring.D mol deionized water is taken, adjusting pH value with glacial acetic acid is 4.(wherein: b/c=23, c/d=6)
3. the mixed liquor of glacial acetic acid and water, which is slowly dropped to solution A, forms mixed solution, stop stirring, in mixed liquor
Carbon nanotube after a g sulfuric acid treatment is put into, ultrasonic disperse becomes gel to it under 80kHz.After gel is almost dry, put
Enter to completely cut off air in tube furnace and obtains composite carried catalyst with 500 DEG C of roasting 270min.(wherein: a/ (79.87b)=1)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 90min, Ofloxacin conversion ratio is that 39%, TOC removal rate is 25%.
Comparative example 7:
1. taking carbon nanotube, it is totally submerged, after impregnating 20h, is filtered, drying with deionized water.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 150rpm
Revolving speed stirring.By Ni (NO3)2·6H2O and Ce (NO3)3·6H2O is dissolved in d mol deionized water and forms solution B, with ice vinegar
Acid for adjusting pH value is 3.(wherein: b/c=26, c/d=8)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, is put at a g in AB mixed liquor
Carbon nanotube after reason, ultrasonic disperse becomes gel to it under 90kHz.After gel is almost dry, it is put into tube furnace interval
Exhausted air obtains composite carried catalyst with 500 DEG C of roasting 300min, its active component NiO load capacity is in terms of metal
1.0wt.%, CeO2Load capacity is 1.0wt.%.(wherein: a/ (79.87b)=1)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 90min, Ofloxacin conversion ratio is that 66%, TOC removal rate is 56%.
Comparative example 8:
1. taking carbon nanotube, it is totally submerged with 50% concentrated nitric acid, is acidified 20h.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 200rpm
Revolving speed stirring.By Ce (NO3)3·6H2O is dissolved in d mol deionized water and forms solution B, and adjusting pH value with glacial acetic acid is 6.
(wherein: b/c=25, c/d=5)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g nitre is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 90kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 650 DEG C of roasting 280min, its active component CeO in terms of metal2Load capacity is
2.0wt.%.(wherein: a/ (79.87b)=0.5)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 90min, Ofloxacin conversion ratio is that 63%, TOC removal rate is 55%.
Comparative example 9:
1. taking carbon nanotube, it is totally submerged with 65% concentrated nitric acid, is acidified 22h.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 200rpm
Revolving speed stirring.By Ni (NO3)2·6H2O is dissolved in d mol deionized water and forms solution B, and adjusting pH value with glacial acetic acid is 3.
(wherein: b/c=24, c/d=7)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g nitre is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 80kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 200 DEG C of roasting 300min, its active component NiO load capacity is in terms of metal
1.0wt.%.(wherein: a/ (79.87b)=1.5)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 90min, Ofloxacin conversion ratio is that 55%, TOC removal rate is 48%.
Comparative example 10:
1. taking carbon nanotube, it is totally submerged with 50% concentrated nitric acid, is acidified 22h.After deionized water is repeatedly washed, filter,
Drying.
2. b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, with magnetic stirring apparatus with 200rpm
Revolving speed stirring.By Ni (NO3)2·6H2O and Co (NO3)2·6H2O is dissolved in d mol deionized water and forms solution B, with ice vinegar
Acid for adjusting pH value is 4.(wherein: b/c=25, c/d=5)
3. solution B, which is slowly dropped to solution A, forms AB mixed solution, stop stirring, a g nitre is put into AB mixed liquor
Carbon nanotube after acid processing, ultrasonic disperse becomes gel to it under 90kHz.After gel is almost dry, it is put into tube furnace
Middle isolation air obtains composite carried catalyst with 500 DEG C of roasting 60min, its active component NiO load capacity is in terms of metal
1.0wt.%, Co3O4Load capacity is 3.0wt.%.(wherein: a/ (79.87b)=0.5)
4. catalytic oxidation experiment condition: composite material carrier catalyst amounts are 0.5g/L, and Ofloxacin is initial
Concentration is 100mg/L, and potassium hydrogen persulfate dosage is 8g/L, and water-bath constant temperature oscillator is anti-with 50 DEG C of water-baths of revolving speed of 150r/min
After answering 90min, Ofloxacin conversion ratio is that 71%, TOC removal rate is 65%.
Conclusion: it can be seen that by above-described embodiment and comparative example
1. composite carried catalyst catalytic activity is higher than single carried catalyst catalytic activity.
2. as nitric acid, sulfuric acid treatment carbon nanotube prepared by composite carried catalyst catalytic activity be higher than it is not acidified
Composite catalyst catalytic activity prepared by the carbon nanotube of processing.
3. the catalyst that the catalyst activity of carrying active substance is higher than unsupported active material.
4. working as catalyst preparation ratio are as follows: c/b=20-30；D/b=5-10；When a/ (79.87b)=0.5-2.5, catalysis
The catalytic activity of agent is higher.(wherein a: acid processing carbon nanotube mass, unit: g；B: the amount of butyl titanate, unit: mol；
C: the amount of dehydrated alcohol, unit: mol)
5. the glacial acetic acid described in the catalyst preparation step 3 adjusts mixed solution pH value when being 3-4, the catalytic activity of catalyst
It is higher.
6. the catalytic activity of catalyst is higher when catalyst maturing temperature is 500-700 DEG C of roasting 240-300min.
Claims (9)
1. a kind of preparation method of titanium dioxide carbon nanotube composite carried catalyst, it is characterised in that:
Step 1, carbon nanotube is dipped to weight percentage 50-70% (most preferably 55-65%) concentrated nitric acid or the concentrated sulfuric acid
It is totally submerged, is acidified 20-30h (most preferably 22-28h)；After deionized water washing, the carbon nanometer on deionized water surface will be floated on
Pipe removal takes lower sediment carbon nanotube to filter, drying；
Step 2, b mol butyl titanate is dissolved in c mol dehydrated alcohol and forms solution A, be placed in magnetic stirring apparatus with 100-
The revolving speed of 200rpm (most preferably 125-180rpm) stirs；
Step 3, one or both of cerous nitrate, cobalt nitrate, bismuth nitrate, nickel nitrate are dissolved in shape in d mol deionized water
At solution B, pH is adjusted with glacial acetic acid；
Step 4, under conditions of magnetic stirring apparatus is stirred continuously, by solution B with 10-20mL/min (most preferably 12-18mL/
Min speed) is slowly dropped to solution A and forms AB mixed solution；
Step 5, stop stirring, carbon nanotube after a g acidification, 60-100kHz (most preferably 70- are put into AB mixed liquor
Ultrasonic disperse under 90kHz) is until it becomes gel；
Step 6, after gel drying, it is put into tubular type kiln roasting, obtains titanium dioxide, carbon nanotube complex carrier efficient catalytic
Agent.
2. preparation method according to claim 1, it is characterised in that: with CeO2、Co3O4、Bi2O3, one of NiO or two
Kind is active material, its activity component load quantity is 1.0~5.0wt.% in terms of metal.
3. preparation method according to claim 1, it is characterised in that: c/b is 20-30, the step 3 in the step 2
In with d/b in step 2 be 5-10.
4. preparation method according to claim 1, it is characterised in that: glacial acetic acid adjusts mixed solution pH in the step 3
Value is 3-4.
5. preparation method according to claim 1, it is characterised in that: the step 2 is with a/ in step 5 (79.87b)
0.5-2.5 (titania molecule amount: 79.87g/mol).
6. preparation method according to claim 1, it is characterised in that: maturing temperature is 500-700 DEG C of roasting in the step 6
Burn 240-300min.
7. a kind of prepared catalyst obtained of any the method for claim 1-6.
8. the application that catalyst described in a kind of claim 7 handles organic wastewater under persulfate oxidation reaction system；
The intermittent reaction condition of the catalyst treatment organic wastewater are as follows: normal pressure, initial pH on wastewater 3-11, reaction temperature are
20-60 DEG C, potassium hydrogen persulfate dosage 6-8g/L, catalyst amounts 0.05-0.5g/L.
9. application according to claim 8, it is characterised in that: the organic wastewater is antibiotics waste water.
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|---|---|---|---|---|
| CN110116019A (en) * | 2019-04-28 | 2019-08-13 | 太原理工大学 | A kind of nano-cobaltic-cobaltous oxide/aluminium oxide@carried catalyst and its preparation method and application |
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