CN109603870A - A kind of bimetallic replaces the preparation and application of solid heteropoly acid salt composite catalyst - Google Patents
A kind of bimetallic replaces the preparation and application of solid heteropoly acid salt composite catalyst Download PDFInfo
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- CN109603870A CN109603870A CN201811560526.XA CN201811560526A CN109603870A CN 109603870 A CN109603870 A CN 109603870A CN 201811560526 A CN201811560526 A CN 201811560526A CN 109603870 A CN109603870 A CN 109603870A
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- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 150000003839 salts Chemical class 0.000 title claims abstract description 30
- 239000007787 solid Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 12
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 238000009938 salting Methods 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- -1 transition metal salt Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940072172 tetracycline antibiotic Drugs 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000002028 Biomass Substances 0.000 abstract 1
- 239000003905 agrochemical Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000006073 displacement reaction Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 239000011973 solid acid Substances 0.000 abstract 1
- 230000003595 spectral effect Effects 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000004098 Tetracycline Substances 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229960002180 tetracycline Drugs 0.000 description 4
- 229930101283 tetracycline Natural products 0.000 description 4
- 235000019364 tetracycline Nutrition 0.000 description 4
- 150000003522 tetracyclines Chemical class 0.000 description 4
- 230000006798 recombination Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 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
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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Materials Engineering (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
A kind of bimetallic replaces the preparation and application of solid heteropoly acid salt composite catalyst, belongs to new energy materials and field of environmental engineering.The present invention makes full use of the separation of charge efficiency of absorbing properties and enhancing of the heteropoly acid in ultraviolet-visible light spectral limit, prepares a series of bimetal solid heteropolyacid salt composite catalysts by way of bimetal salt displacement heteropoly acid proton under hydrothermal conditions.The composite catalyst can be respectively as solid acid and photochemical catalyst, for the catalyzed conversion of biomass and the photocatalytic oxidation degradation of organic pollutant, have the advantages that preparation condition is mild, catalytic activity is high and reusable, it can be applied to the processing of agricultural chemicals waste water, waste water from dyestuff, phenols wastewater etc., provide a kind of new processing technique to reduce sewage middle and high concentration organic pollutant.
Description
Technical field
The invention belongs to environment-friendly engineering technical fields, are related to a kind of preparation method of solid heteropoly acid salt composite catalyst
And its application in organic pollutant light degradation.
Background technique
Photocatalyst is a kind of emerging effective ways for reducing hardly degraded organic substance in environment.In semiconductor light
In catalyst, titanium dioxide (TiO2) since it is with very high photocatalytic activity, high chemical stability, hypotoxicity and low cost
And it is concerned.However, light induced electron and hole-recombination rate height result in lower photo-quantum efficiency.In order to eliminate this disadvantage
End, scientific research personnel is to TiO2Many study on the modification have been carried out, such as metal ion and nonmetallic ion-doped, have been co-deposited metal, and
Other semiconductors couplings carry out dye sensitization and the composite material of Novel Titanium dioxide base etc. in titanium dioxide surface.
In recent years, a large number of studies show that building heterojunction photovoltaic converting system can be improved light induced electron and hole separation energy
Power and transfer ability, so it is to improve the efficiency of solar energy utilization and light that binary or polynary semiconductors coupling, which construct hetero-junctions system,
Urge one of active effective means.Phosphotungstic acid is a kind of heteropoly acid with Keggin-type structure, receives electronics with very strong
Ability, and have the photochemical properties closely similar with semiconductor light-catalyst.Lu et al. (J Hazard Mater, 2012,
A series of H 199-200:1-8) are prepared for using improved sol-gel-hydrothermal and spin-coating method3PW12O40/TiO2Composite membrane
Photochemical catalyst, the catalyst have excellent photocatalytic activity to water-soluble dye rhodamine b under xenon lamp irradiation.Julián A
It is synthesized under high temperature (> 400 DEG C) by sol-gel method Deng (J Photoch Photobio A, 2014,289:22-30)
The TiO of phosphotungstic acid and silicotungstic acid modified2Material, these composite materials show higher photocatalytic activity.However, having reported
Heteropoly acid/TiO2Composite material, preparation process is complicated, energy consumption is high, and heteropoly acid is soluble easily in water is difficult to reuse.For existing
There is the deficiency of preparation process, this patent proposes that a kind of novel dual metal replaces solid heteropoly acid salt composite catalyst, preparation process
Mildly, composite active is high, reusable.
Summary of the invention
For the deficiency of existing preparation process, this patent proposes that a kind of novel dual metal replaces that solid heteropoly acid salt is compound to urge
Agent, heteropoly acid after substitution itself have it is very strong connect nucleophobic ability, it have and semiconductor light-catalyst very phase
As photochemical properties.Further with TiO2After surface recombination, heteropolyacid anions play modification, to capture TiO2It inhales
Electronics caused by photon is received, extends the recombination time again of electron-hole pair, and then improve TiO2Nanoparticle photocatalysis
Efficiency.This method uses mild hydrothermal method, and composite material photocatalytic activity is high, the depth suitable for various waste water
Reason, it is recyclable not generate secondary pollution.
Specific technical solution:
A kind of bimetallic replaces the preparation method of solid heteropoly acid salt composite catalyst, comprising the following steps: by transition gold
Belong to that salt is soluble in water is configured to salting liquid, salting liquid is then added dropwise to heteropoly acid aqueous solution or heteropoly acid and TiO2Mixed liquor
Middle formation mixed solution A obtains mixed solution B, mistake in mixed solution B then to cesium chloride aqueous solution is added dropwise in mixed solution A
The molar ratio for crossing metal salt, cesium chloride and heteropoly acid is 0.25~1:1~2:1, and mixed solution B is milky suspension, and is turned
It moves in reaction kettle, 1~5h of hydro-thermal process at 160 DEG C~220 DEG C is filtered, washed and dried, and is obtained bimetallic and is replaced solid
Heteropolyacid salt composite catalyst.
Above-mentioned transition metal salt is one of stannic chloride, nickel chloride, copper chloride, ferrous chloride, zinc chloride, and heteropoly acid is
One of phosphorus heteropoly tungstic acid, silicotungstic heteropolyacid.
Further, when containing TiO in mixed solution A2When, TiO in mixed solution B2With the molar ratio of heteropoly acid be 10~
100:1。
Heteropoly acid concentration is 5~10g/L in above-mentioned mixed solution B.
The bimetallic of above method preparation replaces the application of solid heteropoly acid salt composite catalyst, includes the following steps: to claim
It takes bimetallic to replace solid heteropoly acid salt composite catalyst, is added in the quartz reactor for filling organic pollutant solution, has
The concentration of machine pollutant solution is 10~100mg/L；Every liter of organic pollutant solution needs bimetallic to replace solid heteropoly acid salt multiple
The dosage for closing catalyst is 0.1~1.5g；0.5h is stirred under subdued light conditions, is then stirred to react 1~5h under ultraviolet light, is examined
Survey and calculate the removal rate of organic pollutant.
Above-mentioned organic pollutant is one of tetracycline antibiotics, Rogor.
Above-mentioned ultraviolet lamp power is 250W, and wavelength 365nm, mixing speed is 50~300r/min.
The invention has the advantages that bimetallic replaces the preparation process of solid heteropoly acid salt composite catalyst simply easy
Realize that unit standardized operation, bimetal solid heteropolyacid salt are nano particle, itself with it is excellent receive electronic capability and
The ability of photooxidation reaction, with TiO2Realize surface recombination, catalyst stabilization during light-catalyzed reaction can be recycled and repeat
It uses, to realize the characteristics of reducing cost, discharge without secondary pollution.
Detailed description of the invention
Attached drawing 1 is the SEM spectrogram that bimetallic nano replaces solid heteropoly acid salt composite catalyst.
Attached drawing 2 is the XRD spectra that bimetallic nano replaces solid heteropoly acid salt composite catalyst.
Specific embodiment
A specific embodiment of the invention is described in detail below in conjunction with technical solution (and attached drawing).
Embodiment one
Prepare SnCl4Aqueous solution, by SnCl4It is water-soluble that phosphorus heteropoly tungstic acid is added dropwise to the molar ratio 0.25:1 of phosphorus heteropoly tungstic acid
In liquid, CsCl solution then is added dropwise by the molar ratio 1.5:1 of CsCl and phosphorus heteropoly tungstic acid, obtains milky suspension, and shift
It into reaction kettle, in 220 DEG C of hydro-thermal process 1h, is filtered, washed and dried, obtains nano-composite catalyst
H0.5Sn0.25Cs1.5PW12O40。
10mg/L tetracycline aqueous solution is prepared, H is added0.5Sn0.25Cs1.5PW12O40, working concentration 0.75g/L, in half-light
Under the conditions of stir 0.5h, be then stirred to react 2.5h under 250W, 365nm ultraviolet light, tetracycline removal rate is 93.3%.
Embodiment two
Prepare SnCl4Aqueous solution, by SnCl4It is water-soluble that phosphorus heteropoly tungstic acid is added dropwise to the molar ratio 0.25:1 of phosphorus heteropoly tungstic acid
In liquid, CsCl solution then is added dropwise by the molar ratio 1:1 of CsCl and phosphorus heteropoly tungstic acid, obtains milky suspension, and be transferred to
It in reaction kettle, in 160 DEG C of hydro-thermal process 5h, is filtered, washed and dried, obtains nano-composite catalyst HSn0.25CsPW12O40。
50mg/L tetracycline aqueous solution is prepared, HSn is added0.25CsPW12O40, working concentration 0.1g/L, in subdued light conditions
Lower stirring 0.5h, is then stirred to react 5h under 250W, 365nm ultraviolet light, and tetracycline removal rate is 79%.
Embodiment three
Prepare SnCl4Aqueous solution, by SnCl4With the molar ratio 0.25:1 of phosphorus heteropoly tungstic acid be added dropwise to phosphorus heteropoly tungstic acid and
TiO2In suspension solution, wherein phosphorus heteropoly tungstic acid and TiO2Molar ratio be 1:100, subsequent rubbing by CsCl and phosphorus heteropoly tungstic acid
CsCl solution is added dropwise than 1:1 in you, obtains milky suspension, and be transferred in reaction kettle, in 200 DEG C of hydro-thermal process 2h, filter,
It washs and dries, obtain nano-composite catalyst HSn0.25CsPW12O40/TiO2, SEM spectrogram is shown in attached drawing 1, and XRD spectra is shown in attached
Fig. 2.
15mg/L Rogor aqueous solution is prepared, HSn is added0.25CsPW12O40, working concentration 1g/L stirs under subdued light conditions
0.5h is mixed, 2h is then stirred to react under 250W, 365nm ultraviolet light, Rogor removal rate is 93%.
Example IV
Prepare NiCl2Aqueous solution, by NiCl2Silicotungstic heteropolyacid and TiO are added dropwise to the molar ratio 1:1 of silicotungstic heteropolyacid2It is outstanding
In turbid solution, wherein silicotungstic heteropolyacid and TiO2Molar ratio be 1:10, then press CsCl and silicotungstic heteropolyacid molar ratio 1:1
CsCl solution is added dropwise, obtains milky suspension, and be transferred in reaction kettle, in 200 DEG C of hydro-thermal process 2h, is filtered, washed simultaneously
It is dry, obtain nano-composite catalyst NiCsPW12O40/TiO2。
15mg/L Rogor aqueous solution is prepared, NiCsPW is added12O40/TiO2, working concentration 1g/L stirs under subdued light conditions
0.5h is mixed, 2h is then stirred to react under 250W, 365nm ultraviolet light, Rogor removal rate is 89%.
Claims (8)
1. the preparation method that a kind of bimetallic replaces solid heteropoly acid salt composite catalyst, which comprises the following steps:
Salting liquid is configured to by transition metal salt is soluble in water, then by salting liquid be added dropwise to heteropoly acid aqueous solution or heteropoly acid with
TiO2Mixed liquor in form mixed solution A, then in mixed solution A be added dropwise cesium chloride aqueous solution obtain mixed solution B, mix
The molar ratio for closing transition metal salt, cesium chloride and heteropoly acid in solution B is 0.25~1:1~2:1, and mixed solution B is milky
Suspension, and be transferred in reaction kettle, 1~5h of hydro-thermal process at 160 DEG C~220 DEG C is filtered, washed and dried, and is obtained double
Metal Substitutional Solid heteropolyacid salt composite catalyst.
2. a kind of bimetallic according to claim 1 replaces the preparation method of solid heteropoly acid salt composite catalyst, special
Sign is that the transition metal salt is one of stannic chloride, nickel chloride, copper chloride, ferrous chloride, zinc chloride, and heteropoly acid is
One of phosphorus heteropoly tungstic acid, silicotungstic heteropolyacid.
3. a kind of bimetallic according to claim 1 or 2 replaces the preparation method of solid heteropoly acid salt composite catalyst,
It is characterized in that, when containing TiO in mixed solution A2When, TiO in mixed solution B2Molar ratio with heteropoly acid is 10~100:1.
4. a kind of bimetallic according to claim 1 or 2 replaces the preparation method of solid heteropoly acid salt composite catalyst,
It is characterized in that, heteropoly acid concentration is 5~10g/L in mixed solution B.
5. a kind of bimetallic according to claim 3 replaces the preparation method of solid heteropoly acid salt composite catalyst, special
Sign is that heteropoly acid concentration is 5~10g/L in mixed solution B.
6. the bimetallic of any the method preparation of claim 1-5 replaces the application of solid heteropoly acid salt composite catalyst,
It is characterized in that, includes the following steps:
It weighs bimetallic and replaces solid heteropoly acid salt composite catalyst, be added to the quartz reactor for filling organic pollutant solution
In, the concentration of organic pollutant solution is 10~100mg/L；Every liter of organic pollutant solution needs bimetallic to replace solid heteropoly acid
The dosage of salt composite catalyst is 0.1~1.5g；0.5h is stirred under subdued light conditions, then it is stirred to react 1 under ultraviolet light~
5h detects and calculates the removal rate of organic pollutant.
7. the application that bimetallic according to claim 6 replaces solid heteropoly acid salt composite catalyst, which is characterized in that have
Machine pollutant is one of tetracycline antibiotics, Rogor.
8. bimetallic according to claim 6 or 7 replaces the application of solid heteropoly acid salt composite catalyst, feature exists
In ultraviolet lamp power is 250W, and wavelength 365nm, mixing speed is 50~300r/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113336308A (en) * | 2021-04-28 | 2021-09-03 | 昆明理工大学 | Method for degrading and recycling antibiotic wastewater |
| CN116532159A (en) * | 2022-01-25 | 2023-08-04 | 海南师范大学 | Preparation method and application of Keggin type transition metal heteropolyacid salt modified photocatalyst |
| CN117839636A (en) * | 2024-03-06 | 2024-04-09 | 金满塘(天津)生物科技有限公司 | Treatment agent and treatment method for eutrophic cultivation wastewater |
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| CN117839636B (en) * | 2024-03-06 | 2024-05-07 | 金满塘(天津)生物科技有限公司 | Treatment agent and treatment method for eutrophic cultivation wastewater |
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