CN108654670B - Method for treating arylamine pharmaceutical wastewater by using carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles - Google Patents
Method for treating arylamine pharmaceutical wastewater by using carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 43
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002351 wastewater Substances 0.000 title claims abstract description 30
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 19
- XWMVIJUAZAEWIE-UHFFFAOYSA-N 2,5-bis(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=CC=C1C(F)(F)F XWMVIJUAZAEWIE-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000015556 catabolic process Effects 0.000 claims abstract description 30
- 238000006731 degradation reaction Methods 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 235000015110 jellies Nutrition 0.000 claims description 6
- 239000008274 jelly Substances 0.000 claims description 6
- 238000006303 photolysis reaction Methods 0.000 claims description 6
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000005273 aeration Methods 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- LXEKVMQAXWKLPJ-UHFFFAOYSA-N methanol;1,3,5-triazine-2,4,6-triamine Chemical compound OC.NC1=NC(N)=NC(N)=N1 LXEKVMQAXWKLPJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 39
- 239000011787 zinc oxide Substances 0.000 abstract description 18
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 17
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 7
- 230000000593 degrading effect Effects 0.000 abstract description 6
- 238000003980 solgel method Methods 0.000 abstract description 4
- 229920000877 Melamine resin Polymers 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002265 prevention Effects 0.000 abstract description 3
- 238000003911 water pollution Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- JWJOTENAMICLJG-QWBYCMEYSA-N dutasteride Chemical compound O=C([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)N[C@@H]4CC3)C)CC[C@@]21C)NC1=CC(C(F)(F)F)=CC=C1C(F)(F)F JWJOTENAMICLJG-QWBYCMEYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 5
- 229960004199 dutasteride Drugs 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- -1 arylamine compounds Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 238000001782 photodegradation Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 208000028659 discharge Diseases 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000002306 biochemical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229940113178 5 Alpha reductase inhibitor Drugs 0.000 description 1
- 239000002677 5-alpha reductase inhibitor Substances 0.000 description 1
- 206010004446 Benign prostatic hyperplasia Diseases 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 208000004403 Prostatic Hyperplasia Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940054749 avodart Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 210000004914 menses Anatomy 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention belongs to the technical field of water pollution prevention and control, and particularly relates to a method for treating arylamine pharmaceutical wastewater by using carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles. According to the method, melamine is used as a carbon source and a nitrogen source to form graphite-phase carbon nitride through high-temperature calcination, then nano zinc oxide is loaded on the graphite-phase carbon nitride to form zinc oxide-loaded graphite-phase carbon nitride nano particles (ZnO @ g-C3N 4), and finally, the carbon-nitrogen-doped zinc-titanium bimetallic nano particles with the photocatalytic performance are prepared through a sol-gel method. The carbon-nitrogen-doped zinc-titanium bimetallic nano-particle prepared by the method can realize good degradation rate on 2, 5-bis (trifluoromethyl) aniline under a weak acid condition, can be used for degrading other arylamine wastewater, and has an industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of water pollution prevention and control, and particularly relates to a method for treating arylamine pharmaceutical wastewater by using carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles.
Background
Dutasteride, chemically known as (5 α,17 β) -N- [2, 5-bis (trifluoromethyl) phenyl ] -3-oxo-4-azaandrost-1-ene-17-carboxamide, is a dual 5 α -reductase inhibitor developed by Glaxo Smith Kline, uk, approved by the FDA in the us 6 menses, 2003, for use in the prevention and treatment of benign prostatic hyperplasia under the trade name Avodart. CFDA on 03/06/2014 endorsed the sale of this drug in the chinese market.
In the production of dutasteride, aniline derivative 2, 5-bis (trifluoromethyl) aniline is used as a key intermediate, and the molar ratio usage amount of the intermediate in the reaction is greatly higher than that of another structural fragment (Chinese medicine industry journal, 2013,44 (10): 966-968, synthesis of dutasteride), so that a large amount of 2, 5-bis (trifluoromethyl) aniline remains in the reaction liquid. The arylamine compounds have high toxicity and have teratogenic or carcinogenic effects on human bodies. Strict discharge standards of arylamine (such as aniline, p-nitroaniline, diphenylamine and the like) are established in many countries, and the mass concentration of the secondary discharge standard of arylamine compound wastewater is less than or equal to 2mg/L according to the comprehensive sewage discharge standard of China. Therefore, the treatment of industrial wastewater containing aromatic amine compounds is a very important problem.
The common methods for treating the arylamine wastewater comprise a physical method, a biochemical method and a chemical method, wherein activated carbon in the physical method is an adsorbent commonly adopted in the current wastewater treatment, can be used for treating various types of wastewater, but the regeneration and recycling of the activated carbon are complex. When the wastewater is treated, secondary pollution is easily caused in the solvent recovery process by adopting a solvent extraction method. The biochemical method has poor effect on treating the waste water with high concentration due to strong toxicity and poor biodegradability of the arylamine waste water.
The chemical method takes a Fenton and similar Fenton oxidation method as an important method in the advanced oxidation technology, and the Fenton reaction utilizes Fe2+Catalysis H2O2OH free radicals are generated by decomposition, thereby initiating the oxidative degradation reaction of organic matters. The Fenton method is widely applied to the advanced oxidation treatment research of various organic wastewater because of the advantages of mild reaction conditions, simple operation, low cost, environmental friendliness and the like, but the defects that the catalyst cannot be recycled and secondary pollution caused by the loss of the catalyst is the main defect.
Among the various semiconductor photocatalysts, Ti0 is used2Has the unique advantages of high photocatalytic activity, relatively low price, strong stability and the like, and is widely concerned by scholars at home and abroad. But instead of the other end of the tube，Ti02The photocatalysis is low in quantum effect and photocatalytic activity, and the utilization of light is concentrated in an ultraviolet light area; and the powdery catalyst is not easy to recycle when in application, is easy to cause secondary pollution and the like, which are main problems restricting the development of the catalyst.
No literature reports a treatment method of 2, 5-bis (trifluoromethyl) aniline in dutasteride wastewater, so that the search for a cleaning treatment process capable of effectively degrading the 2, 5-bis (trifluoromethyl) aniline in the dutasteride wastewater has practical significance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for treating arylamine pharmaceutical wastewater by using carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles3N4) Finally, the carbon-nitrogen doped zinc-titanium bimetallic nanoparticles with the photocatalytic performance are prepared by a sol-gel method. The carbon-nitrogen-doped zinc-titanium bimetallic nano-particle prepared by the method can realize good degradation rate on 2, 5-bis (trifluoromethyl) aniline under a weak acid condition, can be used for degrading other arylamine wastewater, and has an industrial application prospect.
According to one aspect of the invention, the invention provides a preparation method of zinc-titanium bimetallic nanoparticles doped with carbon and nitrogen, which comprises the following steps:
1)ZnO@g-C3N4the preparation of (1): putting 6.5g zinc powder into 1mol/L sodium hydroxide aqueous solution, then dripping 30ml 30wt% hydrogen peroxide aqueous solution, reacting for 18-20h at 60-70 ℃ in a stainless steel hydrothermal reaction kettle with a tetrafluoroethylene lining, then adding 200ml of 2mol/L melamine methanol solution, reacting for 6-8h at 120 ℃ under 100-90 ℃, finally putting in a closed crucible, calcining for 4-6h at 600 ℃ under the atmosphere of nitrogen, cooling to room temperature after the calcination is finished, washing with absolute ethyl alcohol, and drying to obtain the zinc oxide loaded graphite phase carbon nitride nano-particles (abbreviated as ZnO @ g-C)3N4) (ii) a The invention relates to trimerizationThe graphite phase carbon nitride (g-C) is formed by taking cyanamide as a carbon source and a nitrogen source and calcining at high temperature3N4) Oxidizing the zinc powder by using hydrogen peroxide to obtain zinc oxide, so that the zinc oxide is loaded on the graphite-phase carbon nitride material; in addition, the addition of the hydrogen peroxide in the invention can not only convert the zinc powder into zinc oxide, but also can lead the amino group in the melamine and the hydrogen peroxide to form MHP (cyanamide-hydrogen peroxide) through the generated hydrogen bond, and then the supermolecule aggregate is obtained by using 550-600 ℃ high-temperature calcination while continuously turning on nitrogen, so that the prepared graphite-phase carbon nitride achieves the purpose of oxygen doping, and the modified material has catalytic performance;
2) titanium oxide supporting step: dissolving 10mmol of tetraisopropyl titanate in isopropanol, adding graphite-phase carbon nitride nanoparticles loaded by zinc oxide, stirring and dispersing uniformly, then dropwise adding 20ml of 0.5mol/L nitric acid aqueous solution, stirring for 8-10h at 60-70 ℃ after dropwise adding is finished, and removing the solvent to obtain brown colloid; calcining the jelly at high temperature in an argon atmosphere, cooling to room temperature after calcining, performing ultrasonic treatment on the mixture at the temperature of between 60 and 70 ℃ for 10 to 12 hours by using methylbenzene, and filtering and drying to obtain carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles; the invention uses tetraisopropyl titanate as a precursor to prepare TiO by a sol-gel method2Taking graphite-phase carbon nitride nano-particles loaded by zinc oxide as a carrier, and forming TiO2And loading the nano-particles on graphite-phase carbon nitride in situ to form the carbon-nitrogen-doped zinc-titanium bimetallic nano-particles.
Preferably, the adding amount of the graphite phase carbon nitride nano-particles loaded by the zinc oxide in the step 2) is 15-25 g;
preferably, the temperature for calcining the jelly in the step 2) at high temperature in the argon atmosphere is 600-700 ℃; the final calcination is to eliminate pores in the gel, and the calcination temperature determines the appearance of the finally formed carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles, thereby influencing the catalytic activity of the nanoparticles.
According to another aspect of the invention, the invention provides a use of the zinc-titanium bimetallic nano-particles doped with carbon and nitrogen for degrading arylamine wastewater under the irradiation of ultraviolet light and/or visible light.
Preferably, the aromatic amine is 2, 5-bis (trifluoromethyl) aniline; the specific scheme of the carbon-nitrogen-doped zinc-titanium bimetallic nanoparticle for degrading 2, 5-bis (trifluoromethyl) aniline under the irradiation of ultraviolet light and/or visible light is as follows: adding carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles into the wastewater of the 2, 5-bis (trifluoromethyl) aniline, stirring and dispersing, carrying out photolysis on the wastewater of the 2, 5-bis (trifluoromethyl) aniline by adopting ultraviolet light and/or visible light under the aeration condition, and filtering and recovering the carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles through a microporous filter membrane when the degradation rate of the 2, 5-bis (trifluoromethyl) aniline is not changed any more by HPLC (high performance liquid chromatography).
Preferably, the pH of the wastewater of the 2, 5-bis (trifluoromethyl) aniline is 6.0 +/-0.5; the pH value of the reaction liquid in the photocatalytic reaction influences the surface potential of the zinc-titanium bimetallic nano-particles doped with carbon and nitrogen, thereby influencing the generation of hydroxyl radicals; generally, organic amine substances are easy to degrade under the alkalescent condition, probably because the amine substances and acid form salts under the acidic condition to influence the degradation; however, in the present invention, the optimum degradation effect was obtained at a pH of 6.0 or so.
Preferably, the wastewater of the 2, 5-bis (trifluoromethyl) aniline is photolyzed by ultraviolet light and/or visible light, wherein the photolysis temperature is 40-45 ℃; the degradation rate is slow under the low temperature condition, the degradation rate is not obviously increased any more when the temperature is higher than 50 ℃, and the photolysis temperature is determined to be 40-45 ℃ in order to save energy consumption.
Preferably, the initial concentration of the wastewater of 2, 5-bis (trifluoromethyl) aniline with pH of 6.0 +/-0.5 in the invention is 80-100mg/L, and the weight of the carbon-nitrogen doped zinc-titanium bimetallic nanoparticles added in the wastewater of 2, 5-bis (trifluoromethyl) aniline with pH of 6.0 +/-0.5 per liter is 0.04-0.2 g;
the zinc-titanium bimetallic nano-particles doped with carbon and nitrogen prepared by the method can also degrade other scheme compounds such as aniline, p-nitroaniline and diphenylamine under visible light.
Compared with the prior art, the invention has the following advantages:
1) the method takes melamine as a carbon source and a nitrogen source to form graphite phase carbon nitride through high-temperature calcination, and then the graphite phase carbon nitride is loadedFormation of Zinc oxide loaded graphite phase carbon nitride nanoparticles (ZnO @ g-C) from Nano Zinc oxide3N4) Finally, preparing the carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles with the photocatalytic performance by a sol-gel method; the defect that the traditional nano titanium dioxide can not be used in a visible light area is overcome, and the catalytic efficiency in an ultraviolet light area is improved;
2) the zinc-titanium bimetallic nano-particle doped with carbon and nitrogen prepared by the invention has excellent photocatalytic performance, can degrade 2, 5-bis (trifluoromethyl) aniline under ultraviolet and/or visible light, and has the degradation rate of over 99 percent;
3) the zinc-titanium bimetallic nano-particles doped with carbon and nitrogen prepared by the method can also be used for photocatalytic degradation of aniline, p-nitroaniline and diphenylamine, and the application range of the catalyst is wider;
4) the zinc-titanium bimetallic nano-particles doped with carbon and nitrogen prepared by the method can be recycled and reused, and the performance of catalyzing and degrading arylamine after being used for three times is not obviously reduced; after five times of use, the catalyst can be activated by combining acid impregnation and calcination.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention.
Example 1
The carbon-nitrogen doped zinc-titanium bimetallic nano-particles are prepared by the following method:
1)ZnO@g-C3N4the preparation of (1): putting 6.5g zinc powder into 50ml of 1mol/L sodium hydroxide aqueous solution, then dropwise adding 30ml of 30wt% hydrogen peroxide aqueous solution, reacting for 18-20h at 60-70 ℃ in a stainless steel hydrothermal reaction kettle with a tetrafluoroethylene lining, then adding 200ml of 2mol/L melamine methanol solution, reacting for 6-8h at 100-120 ℃, finally putting the mixture into a closed crucible, calcining for 4-6h at 550-600 ℃ in a nitrogen atmosphere, cooling to room temperature after the calcination is finished, washing with anhydrous ethanol, and drying at 60 ℃ to obtain the zinc oxide-loaded graphite-phase carbon nitride nanoparticlesPellets (abbreviated as ZnO @ g-C)3N4)；
2) Titanium oxide supporting step: 10mmol of tetraisopropyl titanate was dissolved in 100ml of isopropanol, and 20g of zinc oxide-loaded graphite-phase carbon nitride nanoparticles (abbreviated as ZnO @ g-C) were added3N4) Stirring and dispersing uniformly, then dropwise adding 20ml of 0.5mol/L nitric acid aqueous solution, stirring for 8-10h at 60-70 ℃ after dropwise adding is finished, and removing the solvent to obtain brown jelly; calcining the jelly at high temperature for 6h in argon atmosphere, cooling to room temperature after calcining, performing ultrasonic treatment on the mixture at 60-70 ℃ for 10-12h by using toluene, filtering and drying to obtain the carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles.
The carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles prepared at different calcination temperatures in the step 2) are abbreviated as Cat/X, and X represents different calcination temperatures.
Example 2
The Cat-X obtained in example 1 at different calcination temperatures was used as a photocatalyst to photodegrade 2, 5-bis (trifluoromethyl) aniline by the following process:
adding 500ml of 2, 5-bis (trifluoromethyl) aniline aqueous solution (prepared by preparing 2, 5-bis (trifluoromethyl) aniline standard substance and water into 10mg/L aqueous solution, and adjusting pH to 7.0) into a multipurpose flange-type internal reaction reactor IFA300 (Beijing Pofely science and technology Co., Ltd.), and respectively adding Cat/X and nano TiO prepared in example 1 at different calcination temperatures2And nano ZnO particles of 20mg respectively, irradiating with 300W microsporan 300 xenon lamp (Beijing Pofely science and technology Co., Ltd.) light source simulating visible light at 30 ℃, continuously aerating while irradiating, detecting the concentration of 2, 5-bis (trifluoromethyl) aniline by HPLC sampling every 1h, stopping irradiation when the concentration of the two samples does not change, and counting the photocatalytic degradation rate of the 2, 5-bis (trifluoromethyl) aniline in each catalytic system as shown in Table 1:
TABLE 1 photodegradation rates of different catalysts for 2, 5-bis (trifluoromethyl) aniline
| Catalyst and process for preparing same | NA | TiO2 | ZnO | Cat/250 | Cat/450 | Cat/550 | Cat/650 | Cat/750 | Cat/850 |
| Percent of degradation/%) | 23.2 | 30.3 | 44.6 | 65.2 | 69.8 | 76.4 | 89.2 | 83.4 | 65.2 |
Note: NA stands for no catalyst added, only illumination and aeration.
The above results show that the effects of light irradiation and aeration alone can be achieved without adding a catalyst2, 5-bis (trifluoromethyl) aniline is degraded, but the degradation rate is lower and is only 23.2%; adding TiO2The failure to effectively increase the degradation rate is mainly due to TiO2The visible light cannot be effectively utilized; ZnO nanoparticles vs. TiO2The degradation rate of the 2, 5-bis (trifluoromethyl) aniline is improved to 44.6 percent, but the degradation rate still needs to be improved without industrial application prospect; the Cat/X-ray degradability obtained at different calcination temperatures is different, and the degradation property obtained at the calcination temperature of 650 ℃ is the most excellent.
Example 3
The Cat/650 is used as a photodegradation catalyst, degradation rates under different pH environments, different Cat/650 dosage and different initial concentrations of 2, 5-bis (trifluoromethyl) aniline aqueous solution are examined, and the test scheme is as follows:
adding 500ml of 2, 5-bis (trifluoromethyl) aniline aqueous solution (self-made, adopting 2, 5-bis (trifluoromethyl) aniline standard and water to prepare aqueous solutions with different concentrations, adopting hydrochloric acid or sodium hydroxide to adjust the pH value to different pH values) into a multipurpose flange-type internal illumination reactor IFA300 (Beijing Pofely science and technology Co., Ltd.), respectively adding different weights of Cat/650 prepared in example 1, adopting a 300W Microcor 300 xenon lamp (Beijing Pofely science and technology Co., Ltd.) light source to simulate visible light to irradiate at 40-45 ℃, continuously aerating while irradiating, sampling by HPLC every 1h to detect the concentration of 2, 5-bis (trifluoromethyl) aniline, when the concentration of the samples sampled in the two times does not change any more, stopping irradiation, and counting the photocatalytic degradation rate of the 2, 5-bis (trifluoromethyl) aniline in each catalytic system, wherein the photocatalytic degradation rate is shown in table 2:
TABLE 2 Effect of different influencing factors on the degradation Rate
Example 4
After the photocatalytic degradation is finished, filtering and separating Cat/650 by using a nanofiltration membrane, washing with acetone, drying at 50 ℃ under reduced pressure to constant weight, performing a recovery and reuse test, wherein the relationship between the use frequency and the degradation rate of 2, 5-bis (trifluoromethyl) aniline is shown in Table 3, and the photodegradation process operation is performed according to the process conditions in the sequence 17 in Table 2:
TABLE 3 relationship between Cat/650 usage times and degradation rate
| Number of times of use | R-1 | R-2 | R-3 | R-4 | R-5 |
| Rate of degradation | 99.9 | 99.2 | 98.9 | 92.3 | 86.6 |
Note: r-1 represents the condition of first recovery and reuse.
The results show that the photocatalytic performance of Cat/650 is not obviously reduced when the Cat/650 is recycled and reused for the first three times, the photocatalytic performance is obviously reduced after the Cat/650 is used for the fourth time, the degradation rate of the 2, 5-bis (trifluoromethyl) aniline is reduced to 86.6 percent after the Cat/650 is used for the fifth time, and the 2, 5-bis (trifluoromethyl) aniline cannot be recycled and reused.
In order to solve the problem of the degradation performance of Cat/650 photocatalysis, the following activation method is carried out on the recovery of Cat/650 after four times of use in the invention:
first, calcination activation
The heterogeneous catalyst can be activated in catalytic performance by a calcination method, the recovered Cat/650 is calcined for 6h at 650 ℃ in a nitrogen atmosphere, then the temperature is reduced to room temperature, and the 2, 5-bis (trifluoromethyl) aniline is tested by adopting the process conditions in the sequence 17 in the table 2, wherein the degradation rate of the 2, 5-bis (trifluoromethyl) aniline is 79.2 percent, the activity of the catalyst is not improved, and the catalyst tends to be reduced.
Two, acid impregnation and calcination are combined
Putting the recovered Cat/650 into 0.5mol/L hydrochloric acid aqueous solution, ultrasonically dipping for 2-3h at room temperature, filtering, washing with water, drying, calcining for 6h at 650 ℃ in nitrogen atmosphere, cooling to room temperature to obtain activated Cat/650, and testing 2, 5-bis (trifluoromethyl) aniline by adopting the process conditions in the sequence 17 in the table 2, wherein the degradation rate of the 2, 5-bis (trifluoromethyl) aniline is 99.2%, so that the activation effect is achieved.
Example 5
Adopting freshly prepared Cat/650 as a photodegradation catalyst, preparing aniline, p-nitroaniline and diphenylamine standard substances into aqueous solutions with the concentration of 50mg/L by using water respectively, and investigating the photocatalytic effect, wherein the process conditions are as follows
Adding 500ml of 50mg/L arylamine aqueous solution (self-made, hydrochloric acid or sodium hydroxide is adopted to adjust the pH to 6.5 or 8.0) into a multipurpose flange-type internal irradiation reactor IFA300 (Beijing Pofely science and technology Limited company), adding 20mg of freshly prepared Cat/650, adopting a 300W Microlar 300 xenon lamp (Beijing Pofely science and technology Limited company) light source to simulate visible light to irradiate at 40-45 ℃, continuously aerating while irradiating, detecting the arylamine concentration by HPLC sampling every 1h, stopping irradiation when the concentrations of the two subsequent samples are not changed any more, and counting the photocatalytic degradation rate of each arylamine in each catalytic system as shown in Table 4:
TABLE 4 degradation Effect of different aromatic amine derivatives at different pH values
For an aniline solution, the degradation effect is optimal under a weak acid condition, and the result is consistent with that of 2, 5-bis (trifluoromethyl) aniline; the degradation rate of p-nitroaniline is optimal under alkalescence (pH 8.0), but is only 83.2%, and further optimization is needed in the later period; the diphenylamine solution can realize good degradation rate under the conditions of weak acid or weak base, so that the application range of the catalyst is wider, and the catalyst can be suitable for degradation under different water qualities in the later period.
Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (4)
1. The application of the zinc-titanium bimetallic nano-particle doped with carbon and nitrogen is characterized in that: the degradation of arylamine wastewater is carried out under the irradiation of ultraviolet light and/or visible light;
the arylamine is 2, 5-bis (trifluoromethyl) aniline;
the method comprises the following specific steps: adding carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles into the wastewater of the 2, 5-bis (trifluoromethyl) aniline, stirring and dispersing, carrying out photolysis on the wastewater of the 2, 5-bis (trifluoromethyl) aniline by adopting ultraviolet light and/or visible light under the aeration condition, and filtering and recovering the carbon-nitrogen-doped zinc-titanium bimetallic nanoparticles through a microporous filter membrane when the degradation rate of the 2, 5-bis (trifluoromethyl) aniline is not changed any more by HPLC (high performance liquid chromatography) detection;
the pH value of the wastewater of the 2, 5-bis (trifluoromethyl) aniline is 6.0 +/-0.5;
the carbon-nitrogen-doped zinc-titanium bimetallic nanoparticle is prepared by the following preparation method, and comprises the following steps:
1）ZnO@g-C3N4the preparation of (1): putting 6.5g of zinc powder into 1mol/L of sodium hydroxide aqueous solution, then dropwise adding 30mL of 30wt% hydrogen peroxide aqueous solution, reacting for 18-20h at 60-70 ℃ in a stainless steel hydrothermal reaction kettle with a tetrafluoroethylene lining, then adding 200mL of 2mol/L melamine methanol solution, reacting for 6-8h at 120 ℃ under 100-3N4；
2) Titanium oxide supporting step: dissolving 10mmol of tetraisopropyl titanate in isopropanol, adding ZnO @ g-C3N4Stirring and dispersing uniformly, then dropwise adding 20mL of 0.5mol/L nitric acid aqueous solution, stirring for 8-10h at 60-70 ℃ after dropwise adding is finished, and removing the solvent to obtain brown jelly; calcining the jelly in argon atmosphere at 600-700 ℃, cooling to room temperature after calcining, performing ultrasonic treatment on the mixture at 60-70 ℃ for 10-12h by using toluene, filtering and drying to obtain the carbon-nitrogen-doped zinc-titanium bimetallic nano-particles.
2. Use according to claim 1, characterized in that: ZnO @ g-C in step 2)3N4The amount of (A) is 15-25 g.
3. Use according to claim 1, characterized in that: performing photolysis on the wastewater of the 2, 5-bis (trifluoromethyl) aniline by adopting ultraviolet light and/or visible light, wherein the photolysis temperature is 40-45 ℃.
4. Use according to claim 3, characterized in that: the initial concentration of the waste water of the 2, 5-bis (trifluoromethyl) aniline with the pH value of 6.0 +/-0.5 is 80-100mg/L, and the weight of the zinc-titanium bimetallic nano particles doped with carbon and nitrogen added into each liter of the waste water of the 2, 5-bis (trifluoromethyl) aniline with the pH value of 6.0 +/-0.5 is 0.04-0.2 g.
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