CN107376891A - Double rare earth codoping titanium oxide catalyst preparation methods of tetracycline wastewater processing - Google Patents
Double rare earth codoping titanium oxide catalyst preparation methods of tetracycline wastewater processing Download PDFInfo
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- CN107376891A CN107376891A CN201710640852.0A CN201710640852A CN107376891A CN 107376891 A CN107376891 A CN 107376891A CN 201710640852 A CN201710640852 A CN 201710640852A CN 107376891 A CN107376891 A CN 107376891A
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- rare earth
- nitrate
- titanium oxide
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- oxide catalyst
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 31
- 239000002351 wastewater Substances 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 239000004098 Tetracycline Substances 0.000 title claims abstract description 24
- 235000019364 tetracycline Nutrition 0.000 title claims abstract description 24
- 150000003522 tetracyclines Chemical class 0.000 title claims abstract description 24
- 229960002180 tetracycline Drugs 0.000 title claims abstract description 23
- 229930101283 tetracycline Natural products 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 21
- 238000012545 processing Methods 0.000 title claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 239000007791 liquid phase Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000012071 phase Substances 0.000 claims abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 239000002086 nanomaterial Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 239000004809 Teflon Substances 0.000 claims description 6
- 229920006362 Teflon® Polymers 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 4
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 3
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229940102396 methyl bromide Drugs 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 230000003115 biocidal effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- -1 rare earth ion Chemical class 0.000 description 3
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of double rare earth codoping titanium oxide catalyst preparation methods with visible light activity of tetracycline wastewater processing, urea, rare earth element nitrate, CTAB are added in ethylene glycol and dissolved, liquid phase titanium source is added in above-mentioned solution afterwards, forms homogeneous phase solution.Then deionized water is added while stirring, forms clear gel.Above-mentioned gel is subjected to hydro-thermal process, washing, filtering and drying, obtains double rare-earth elements doped titanium dioxide photocatalyst afterwards.The voluntarily regulation and control that acid-base value is carried out to reaction system are slowly decomposed by urea in water-heat process, realize purpose of the rare earth element to titanium dioxide codope.The preparation method simple process, Parameter adjustable scope is wide, and repeatability is strong, and cost is low, and obtained titanium dioxide optical catalyst has preferable degradation effect under visible light conditions to tetracycline wastewater.
Description
Technical field
The present invention relates to a kind of double rare earth codoping titanium oxide catalyst preparation methods of tetracycline wastewater processing, and pass through
The product and application that the preparation method obtains.The preparation method can widen the visible light-responded scope of titanium dioxide optical catalyst.
Background technology
With the continuous development of pharmaceuticals industry, China turns into the big production of raw medicine state of the first in the world, due to production technology
And the reason for technology, in antibiotics production there is raw material availability it is low, refine that purity is low, residual fungistatic cellulose content is high in waste water
The problems such as, up to 50,000,000 tons of wastewater flow rate causing domestic 300 Duo Jia antibiotics productions enterprises to discharge every year.Antibiotic waste water
Discharge causes large effect to ecological environment, and being continuously increased of the usage amount of particularly current antibiotic is caused bigger to environment
Influence.Antibiotic is that human treatment's infectious diseases brings huge convenience, has effectively ensured the health of the mankind, but simultaneously by
In the abuse of antibiotic, animal husbandry, culture fishery etc. largely use antibiotic in addition, make antibiotic residual in the environment and
Its caused resistance problems is on the rise, and the negative effect that the mankind and ecological environment bring increasingly is strengthened, threatened
The health of the mankind.Such as hereditary variation, the resistance to the action of a drug, double infection, toxicity, allergic reaction, particularly because the resistance to the action of a drug triggers
Superbacteria occurs, and causes global concern.Therefore, the medical antibiotic contamination in water body environment is removed by ring
Border worker is considered as an important goal in research, how effectively to handle antibiotic residue waste water for improving pharmacy waste water water outlet
The water quality even overall water quality of China is all significant.
For titanium dioxide because chemical property is stable, heat endurance is high, and catalytic activity is high, and anti-light corrosion, nontoxic, raw material is easy to get
The advantages that show one's talent in numerous conductor oxidates, be widely used in air, the degraded of water environment pollution thing, antibacterial, remove
The fields such as smelly and automatically cleaning.But titanium dioxide is as photochemical catalyst that there is also two large problems：First, energy gap causes greatly two
Titanium oxide is extremely low to the utilization rate of sunshine.At normal temperatures, during pH=1, the energy gap of the titanium dioxide of Detitanium-ore-type is about
3.2eV, according to Einstein equation, it can only absorbing wavelength be less than 375nm ultraviolet light, and this part ultraviolet light accounts for sunshine
Gross energy less than 5%.This results in titanium dioxide can not make full use of to being radiated tellurian sunshine, greatly limitation
The use range of catalyst；Secondly, the quantum efficiency of titanium dioxide optical catalyst is too low, light activated electronics and hole life
It is short, it is easily compound, cause most photoproduction load to carry out effective light-catalyzed reaction, this is also to hinder photocatalytic activity
The big limiting factor further improved, the two factors significantly limit its use in actual production and life.
In recent years, people are attempted by metal-doped, nonmetal doping, metal and nonmetallic codope, semiconductors coupling
With the means such as dye photoactivation, the photoresponse scope of titanium dioxide is expanded, suppresses the compound of electronics and hole, so as to improve dioxy
Change the photocatalysis performance of titanium and its compound.
The content of the invention
For overcome the deficiencies in the prior art, present invention aims at provide a kind of double rare earths of tetracycline wastewater processing to be co-doped with
Miscellaneous titanium deoxide catalyst preparation method.
Another object of the present invention is：The product that above-mentioned preparation method obtains is provided.
A further object of the present invention is：The application of the said goods is provided.
The object of the invention is realized by following proposal：
A kind of double rare earth codoping titanium oxide catalyst preparation methods of tetracycline wastewater processing, with titanate esters, cetyl front three
Base ammonium bromide（CTAB）, water, ethylene glycol, urea, rare earth nitrades be raw material, wherein, described titanate esters are liquid phase titanium source, bag
Include following steps：
（1）Urea, CTAB, two kinds of rare earth nitrades are added in ethylene glycol, liquid phase titanium source is added after stirring and dissolving, stirring is formed
Homogeneous phase solution, deionized water is then added dropwise while stirring in above-mentioned system, until formed clear gel, titanate esters and two kinds it is dilute
The mol ratio of native nitrate is 1:0.025:0.025~1:0.15:0.15；
（2）Above-mentioned gel is put into the stainless steel autoclave of teflon lined, at 150 ~ 200 DEG C hydro-thermal reaction 8 ~
Precipitated product is washed with deionized after terminating for 24h, reaction, until the pH of cleaning solution is in neutrality, the then drying at 80 DEG C
More than 10h, processing is dried, dry sample is calcined 2h at 400 DEG C, it is double dilute that removing residual organic matter obtains object
Native codope titanium dioxide composite nano materials.
In the present invention, liquid phase titanium source slowly hydrolyzes to form aqua oxidation titanium gel, and rare earth ion is evenly dispersed in water
Close in titanium oxide gel；By slow decomposition of the urea in hydrothermal reaction process, the acid-base property of system is gradually to alkalescent side
To movement, in situ doping of the thulium in titanium oxide lattice is realized.The preparation method technique and simple flow, ginseng
Number adjustable extent is wide, and repeatability is strong, and cost is low.Slowly decomposed by urea in water-heat process and acid-base value is carried out to reaction system
Voluntarily regulation and control, realize purpose of the rare earth element to titanium dioxide codope.The preparation method technique and simple flow, parameter can
Adjust scope wide, repeatability is strong, and cost is low, and the titanium dioxide optical catalyst of preparation has under visible light conditions to tetracycline wastewater
There is preferable degradation effect.
Described rare earth nitrades are hydration or non-hydrated cerous nitrate, lanthanum nitrate, neodymium nitrate, yttrium nitrate, gadolinium nitrate, nitre
Any two kinds in sour europium, terbium nitrate, samaric nitrate, thulium nitrate, erbium nitrate, ytterbium nitrate.
Titanate esters, CTAB, water, the mol ratio of ethylene glycol and urea are 1：0.5~1：1000~2000：1000~2000：
20~40.
On the basis of such scheme, described liquid phase titanium source refers to：Tetra-n-butyl titanate, isopropyl titanate, metatitanic acid tetrem
The mixture of liquid phase titanium source more than one or both of ester.
The molar ratio of two kinds of rare earth elements is 1:1.
Present invention process is simple, the double rare earth codoped titanium dioxide visible light catalysts obtained by above-mentioned preparation method, carries
High titanium dioxide specific surface area, widens its visible light-responded scope.
There is following mechanism after double rare earth codopes：(a) trap center is formed, valence state is higher than Ti4+Metal ion capture
Electronics, the metal ion capture hole being less than, suppresses e-/h+It is compound；(b) doped energy-band is formed, less energy can excite
Captured on doped energy-band and hole, improve the utilization rate of photon；(c) lattice defect and distortion of lattice are caused, is advantageously formed
More Ti3+Oxidation center, so as to expand the photoresponse scope of titanium dioxide, suppress the compound of electronics and hole, and then improve
The photocatalysis performance of titanium dioxide compound.
Product of the present invention is applied in tetracycline wastewater processing.
Double rare earth codoping titanium oxide catalyst products of tetracycline wastewater processing.
The performance evaluation of double rare earth codoping titanium dioxide nano materials is carried out in quartz glass tube, 100mL tetracyclines
Photochemical catalyst is added in waste water, catalyst amount 1mg/mL, after xenon source catalytic degradation 120min, measure waste water is catalyzed
Front and rear TOC, photocatalytic activity of the photochemical catalyst to tetracycline wastewater is calculated.
The present invention is advantageous in that：Two kinds of equimolar proportion rare earth ions are evenly dispersed in aqua oxidation titanium gel
In, above-mentioned gel is subjected to hydro-thermal process, washing, filtering and drying, obtains double rare-earth elements doped titanium dioxide photocatalyst afterwards
Product.The voluntarily regulation and control that acid-base value is carried out to reaction system are slowly decomposed by urea in water-heat process, realize rare earth element pair
The purpose of titanium dioxide codope.The preparation method simple process, Parameter adjustable scope is wide, and repeatability is strong, and cost is low, is made
Titanium dioxide optical catalyst there is preferable degradation effect under visible light conditions to tetracycline wastewater.
Brief description of the drawings
Fig. 1 is neodymia/yittrium oxide codope titanium dioxide composite nano materials obtained by embodiment 2.
Embodiment
Embodiments of the invention are elaborated below：The present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and operating process, but protection scope of the present invention is not limited to following embodiments：
Embodiment 1
（1）Urea, cetyl trimethylammonium bromide are added in ethylene glycol（CTAB）, cerous nitrate, lanthanum nitrate, after stirring and dissolving
Add liquid phase titanium source（Butyl titanate）, stir and form homogeneous phase solution.Then deionization is added dropwise while stirring in above-mentioned system
Water, until forming clear gel.
（2）Above-mentioned gel is put into the stainless steel autoclave of teflon lined, the hydro-thermal reaction 24h at 150 DEG C.
Reaction terminate after precipitated product is washed with deionized, until cleaning solution pH in neutrality, then at 80 DEG C dry 10h with
On, processing is dried, dry sample is calcined 2h at 400 DEG C, removes residual organic matter, obtain object lanthana/
Cerium oxide codope titanium dioxide composite nano materials.
Wherein, the titanate esters of the addition and CTAB molar ratio are 1:0.5, the molar ratio of titanate esters and water is 1:
2000.The molar ratio of titanate esters and ethylene glycol is 1:1000, the molar ratio of titanate esters and urea is 1:20.Titanate esters and nitre
Sour lanthanum, the molar ratio of cerous nitrate are 1:0.025:0.025.
Photochemical catalyst is 33.6% to tetracycline wastewater TOC degradation rate.
Embodiment 2
（1）Urea, cetyl trimethylammonium bromide are added in ethylene glycol（CTAB）, neodymium nitrate, yttrium nitrate, after stirring and dissolving
Add liquid phase titanium source（Isopropyl titanate）, stir and form homogeneous phase solution.Then deionization is added dropwise while stirring in above-mentioned system
Water, until forming clear gel.
（2）Above-mentioned gel is put into the stainless steel autoclave of teflon lined, the hydro-thermal reaction 8h at 200 DEG C.
Reaction terminate after precipitated product is washed with deionized, until cleaning solution pH in neutrality, then at 80 DEG C dry 10h with
On, processing is dried, dry sample is calcined 2h at 400 DEG C, removes residual organic matter and obtains object neodymia/oxygen
Change yttrium codope titanium dioxide composite nano materials.
Wherein, the titanate esters of the addition and CTAB molar ratio are 1:1, the molar ratio of titanate esters and water is 1:
1000.The molar ratio of titanate esters and ethylene glycol is 1:2000, the molar ratio of titanate esters and urea is 1:20.Titanate esters and nitre
Sour neodymium, the molar ratio of yttrium nitrate are 1:0.05:0.05.
Photochemical catalyst is 36.2% to tetracycline wastewater TOC degradation rate.
Embodiment 3
（1）Urea, cetyl trimethylammonium bromide are added in ethylene glycol（CTAB）, thulium nitrate, gadolinium nitrate, after stirring and dissolving
Add liquid phase titanium source（Tetraethyl titanate）, stir and form homogeneous phase solution.Then deionization is added dropwise while stirring in above-mentioned system
Water, until forming clear gel.
（2）Above-mentioned gel is put into the stainless steel autoclave of teflon lined, the hydro-thermal reaction 12h at 180 DEG C.
Reaction terminate after precipitated product is washed with deionized, until cleaning solution pH in neutrality, then at 80 DEG C dry 10h with
On, processing is dried, dry sample is calcined 2h at 400 DEG C, removes residual organic matter and obtains object thulium oxide/oxygen
Change gadolinium codope titanium dioxide composite nano materials.
Wherein, the titanate esters of the addition and CTAB molar ratio are 1:1, the molar ratio of titanate esters and water is 1:
2000.The molar ratio of titanate esters and ethylene glycol is 1:2000, the molar ratio of titanate esters and urea is 1:40.Titanate esters and nitre
Sour thulium, the molar ratio of gadolinium nitrate are 1:0.15:0.15.
Photochemical catalyst is 44.9% to tetracycline wastewater TOC degradation rate.
Embodiment 4
（1）Urea, cetyl trimethylammonium bromide are added in ethylene glycol（CTAB）, erbium nitrate, ytterbium nitrate, after stirring and dissolving
Add liquid phase titanium source（Isopropyl titanate）, stir and form homogeneous phase solution.Then deionization is added dropwise while stirring in above-mentioned system
Water, until forming clear gel.
（2）Above-mentioned gel is put into the stainless steel autoclave of teflon lined, the hydro-thermal reaction 15h at 160 DEG C.
Reaction terminate after precipitated product is washed with deionized, until cleaning solution pH in neutrality, then at 80 DEG C dry 10h with
On, processing is dried, dry sample is calcined 2h at 400 DEG C, removes residual organic matter and obtains object erbium oxide/oxygen
Change ytterbium codope titanium dioxide composite nano materials.
Wherein, the titanate esters of the addition and CTAB molar ratio are 1:1, the molar ratio of titanate esters and water is 1:
2000.The molar ratio of titanate esters and ethylene glycol is 1:1500, the molar ratio of titanate esters and urea is 1:30.Titanate esters and nitre
Sour erbium, the molar ratio of ytterbium nitrate are 1: 0.05:0.05.
Photochemical catalyst is 41.8% to tetracycline wastewater TOC degradation rate.
Claims (7)
- A kind of 1. double rare earth codoping titanium oxide catalyst preparation methods of tetracycline wastewater processing, with titanate esters, cetyl three Methyl bromide ammonium（CTAB）, water, ethylene glycol, urea, rare earth nitrades be raw material, wherein, described titanate esters are liquid phase titanium source, Comprise the following steps：（1）Urea, CTAB, two kinds of rare earth nitrades are added in ethylene glycol, liquid phase titanium source is added after stirring and dissolving, stirring is formed Homogeneous phase solution, deionized water is then added dropwise while stirring in above-mentioned system, until formed clear gel, titanate esters and two kinds it is dilute The mol ratio of native nitrate is 1:0.025:0.025~1:0.15:0.15；（2）Above-mentioned gel is put into the stainless steel autoclave of teflon lined, at 150 ~ 200 DEG C hydro-thermal reaction 8 ~ Precipitated product is washed with deionized after terminating for 24h, reaction, until the pH of cleaning solution is in neutrality, the then drying at 80 DEG C More than 10h, processing is dried, dry sample is calcined 2h at 400 DEG C, it is double dilute that removing residual organic matter obtains object Native codope titanium dioxide composite nano materials.
- 2. double rare earth codoping titanium oxide catalyst preparation methods of tetracycline wastewater processing according to claim 1, its feature It is, described rare earth nitrades are hydration or non-hydrated cerous nitrate, lanthanum nitrate, neodymium nitrate, yttrium nitrate, gadolinium nitrate, nitric acid Any two kinds in europium, terbium nitrate, samaric nitrate, thulium nitrate, erbium nitrate, ytterbium nitrate.
- 3. double rare earth codoping titanium oxide catalyst preparation methods of tetracycline wastewater processing according to claim 1, its feature It is, it is characterised in that：Titanate esters, CTAB, water, the mol ratio of ethylene glycol and urea are 1：0.5~1：1000~2000：1000 ~2000：20~40.
- 4. the double rare earth codoping titanium oxide catalyst preparation methods handled according to the tetracycline wastewater of claim 1 or 3, it is special Sign is that described liquid phase titanium source refers to：One or both of tetra-n-butyl titanate, isopropyl titanate, tetraethyl titanate with On liquid phase titanium source mixture.
- 5. double rare earth codoping titanium oxide catalyst preparation methods of tetracycline wastewater processing according to claim 1, its feature It is, the molar ratio of two kinds of rare earth elements is 1:1.
- A kind of 6. double rare earth codopes two of the tetracycline wastewater processing obtained according to any preparation methods of claim 1-5 Titanium oxide catalyst product.
- 7. application of the product in tetracycline wastewater processing according to claim 6.
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