CN110127834A - A kind of method that sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant - Google Patents

A kind of method that sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant Download PDF

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Publication number
CN110127834A
CN110127834A CN201910408639.6A CN201910408639A CN110127834A CN 110127834 A CN110127834 A CN 110127834A CN 201910408639 A CN201910408639 A CN 201910408639A CN 110127834 A CN110127834 A CN 110127834A
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China
Prior art keywords
cupric
sulphite
organic pollutant
strengthens
degradable organic
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CN201910408639.6A
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Chinese (zh)
Inventor
孙绍芳
邱立平
张守彬
王嘉斌
谢康
刘贵彩
高明昌
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University of Jinan
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University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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

Abstract

A kind of method that sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant, accelerate conversion of the bivalent cupric ion to univalent copper ion using the reduction of sulphite, and then improve the yield of potentiometric titrations and the degradation efficiency to organic pollutant, the water process specific steps are as follows: pH value is adjusted to 6-11；A certain amount of bivalent cupric ion is added into water sample to be processed, a certain amount of permonosulphuric acid potassium solution and sodium sulfite solution is then added, both can achieve effective degradation to organic contamination after being thoroughly mixed reaction 5-30 minutes.The present invention solves key issues of existing the reaction starting of cupric catalysis persulfate system time length, potentiometric titrations low yield, bivalent cupric ion dosage is big, sludge yield is big.The also active group yield height of the present invention, organic pollutant removal excellent in efficiency, the advantages such as easy to operate, operating cost is low simultaneously.

Description

A kind of sulphite reinforcing cupric catalysis persulfate oxidation degradable organic pollutant Method
Technical field
The present invention designs water treatment field, is specifically related to a kind of sulphite reinforcing cupric catalysis persulfate oxidation The method of degradable organic pollutant.
Background technique
With the enhancing of people's environmental consciousness and the continuous improvement of environmental analysis technology, emerging micro quantity organic pollutant positive day Benefit is specifically included that incretion interferent and drug and use in personal care by global extensive concern, emerging micro quantity organic pollutant Product.Although emerging micro quantity organic pollutant concentration is generally in ng/L- μ g/L in water body, due to emerging micro quantity organic pollutant It is many kinds of, the form with combined pollution, simultaneously because emerging micropollutants are extensively largely using causing its continual It is discharged into water environment, forms " false lasting " property phenomenon in water environment.Emerging micropollutants not only have carcinogenic, cause in water environment The biology toxicological effect such as abnormal and mutagenesis, and persistently seriously threatened in the presence of organism drug resistance formation resistant gene can be enhanced The publilc health in the whole world.
Using hydroxyl radical free radical and potentiometric titrations as the advanced oxidation processes of Typical Representative, pass through oxide of high activity group There is degradation effect well to the especially emerging micropollutants of most pollutants, as further treatment technique in waste water Processing and Water purification field are widely studied.Compared with hydroxyl radical free radical, potentiometric titrations oxidation-reduction potential is higher, Half-life period is more long, lower with water quality background component reactivity, has better choice oxidisability, becomes the heat studied both at home and abroad Point.Current research be mostly using heating, ultraviolet lighting, ultrasound or it is the methods of transition metal-catalyzed activate peroxy-monosulfate or Peroxydisulfate generates potentiometric titrations degradable organic pollutant.Compared with the processing modes such as heating, ultraviolet lighting and ultrasound, Transition metal-catalyzed low energy consumption, the broad interest high-efficient, easy to operate for attracting numerous researchers.Common transition metal ions Including cobalt (Co2+), silver (Ag+), iron (Fe3+), copper (Cu2+), but cobalt and silver itself bio-toxicity it is stronger, limit its Application in practice.The problems such as that there are applicable pH ranges is low again, and sludge yield is big using iron ion catalysis.Copper has with iron phase seemingly Redox property, the solubility with higher under neutral or weak basic condition, therefore new using becoming one in recent years Research hotspot.However since bivalent cupric ion is too slow to univalent copper ion conversion, hence it is evident that constrain cupric/persulfate body It is the yield of potentiometric titrations, leads to that the degradation efficiency of activated by copper ions persulfate system organic matter is low, sludge yield is big. In conclusion improving cupric to cupprous conversion rate, the production of cupric/persulfate system potentiometric titrations is improved Rate is significantly.
Summary of the invention
The present invention is to solve cupric/persulfate system potentiometric titrations low yield, organic pollutant degradation Low efficiency starts key issues of reaction time is long, sludge yield is big, proposes that a kind of quickening cupric is converted to monovalence copper, promotees Into potentiometric titrations yield, the new method of organic pollutant degradation efficiency is improved.
The present invention: a kind of method that sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant, benefit With the reproducibility of sulphite, cupric is quickly reduced to monovalence copper, monovalence copper further activates persulfate and generates sulfuric acid Root free radical cracking organic pollutant is realized particular by following steps:
(1) the water sample pH value to be processed containing organic pollutant is adjusted to 6-11；
(2) a certain amount of bivalent cupric ion is added into water sample to be processed, a certain amount of permonosulphuric acid potassium solution and sulfurous is then added Acid sodium solution both can achieve effective degradation to organic contamination after being thoroughly mixed reaction 5-30 minutes.
Above-mentioned sulfite compound includes one in sodium sulfite, sodium hydrogensulfite, potassium sulfite and potassium bisulfite Kind or several mixtures.
Above-mentioned persulfate is peroxy-monosulfate or peroxydisulfate, and peroxy-monosulfate includes: permonosulphuric acid potassium, crosses one One of sodium sulphate, permonosulphuric acid ammonium are several；Peroxydisulfate includes: permonosulphuric acid potassium, permonosulphuric acid sodium, crosses a sulphur One of sour ammonium is several.
Above-mentioned water sample to be processed can be a variety of different water such as industrial wastewater, sanitary sewage, surface water, landfill leachate Body.
5-40 μM of bivalent cupric ion concentration in above-mentioned water sample to be processed, bivalent cupric ion in solution: sulphite: over cure The reaction molar ratio of hydrochlorate is 1:5-100:10-500.
A kind of sulphite of the present invention strengthens the base of the method for cupric catalysis persulfate oxidation degradable organic pollutant Present principles are: sulphite is reacted with cupric generates monovalence copper and inferior sulfate radical free radical, and monovalence copper can quickly and over cure Hydrochlorate reaction generates potentiometric titrations, while inferior sulfate radical free radical can also react with oxygen and generate potentiometric titrations, from And strengthen the degradation to organic contamination.
A kind of sulphite of the present invention strengthen the method for cupric catalysis persulfate oxidation degradable organic pollutant with The prior art is compared and is had the advantage that
(1) the method for the present invention cupric to cupprous conversion rate faster, hence it is evident that shorten copper catalysis over cure acid system starting when Between, the rate of potentiometric titrations is faster, more efficient, higher to the degradation efficiency of organic pollutant；
(2) the method for the present invention does not need the additional processing modes such as additional progress ultraviolet lighting, heating, ultrasound, normal in room temperature Pressure can carry out, easy to operate, applied widely;
(3) the method for the present invention accelerates the circular response between bivalent cupric ion and univalent copper ion, hence it is evident that reduce cupric from The dosage of son.
Detailed description of the invention
Attached drawing 1 is that a kind of sulphite reinforcing cupric catalysis persulfate oxidation degradation is organic in specific implementation case 1 For the method for pollutant to the degradation effect figure of sulfamethoxazole, zero indicates cupric/peroxy-monosulfate to the oxygen of sulfamethoxazole Change degradation effect；△ indicates sulphite/cupric system to the oxidative degradation effect of sulfamethoxazole；Indicates sulfurous acid Oxidative degradation effect of the salt/cupric/permonosulphuric acid salt system to sulfamethoxazole.
Attached drawing 2 is that a kind of sulphite reinforcing cupric catalysis persulfate oxidation degradation is organic in specific implementation case 2 The method of pollutant is to carbamazepine, oestrone, nonyl phenol, aspirin, chloramphenicol, penicillin, Diclofenac, Nabumetone in water body The differences such as life, brufen, triclosan, Ciprofloxacin, Ofloxacin, Norfloxacin, sulfamethyldiazine, sulfamethazine The degradation effect figure of pollutant.
Specific embodiment
Case study on implementation 1
(1) the sanitary sewage pH value containing sulfamethoxazole is adjusted to 7 using perchloric acid and potassium hydroxide；
(2) 10 μM of copper nitrates are added into water sample to be processed, a certain amount of permonosulphuric acid potassium solution is then added and sodium sulfite is molten Liquid, wherein the ratio of cupric and sodium sulfite and permonosulphuric acid potassium is 1:50:500, is thoroughly mixed, takes in different Sampling point sampling, both can achieve effective degradation to sulfamethoxazole after ten minutes.
A kind of side of sulphite reinforcing cupric catalysis persulfate oxidation degradable organic pollutant in the implementation case Method is as shown in Fig. 1 to the degradation effect of sulfamethoxazole in water body.From attached drawing 1 it is found that cupric/permonosulphuric acid salt system exists Can only degrade in 10 minutes 10% sulfamethoxazole；Sulphite/cupric system removed sulfamethoxazole in 10 minutes Rate only has 20%；And sulphite/cupric/permonosulphuric acid salt system imitated the oxidative degradation of sulfamethoxazole in 10 minutes Fruit reaches 97%；It is above-mentioned the results showed that a kind of sulphite strengthens cupric catalysis persulfate oxidation degrades organic contamination The method of object has good removal effect to sulfamethoxazole.
Case study on implementation 2
Sulfamethoxazole in step (1) is changed into carbamazepine, oestrone, nonyl phenol, aspirin, chlorine in specific implementation case 2 Mycin, penicillin, Diclofenac, naproxen, brufen, triclosan, Ciprofloxacin, Ofloxacin, Norfloxacin, methylene sulfonamide Any one organic pollutant in pyrimidine, sulfamethazine, other steps are identical with case study on implementation 1.
2 sulfite salt of the implementation case strengthens the method pair of cupric catalysis persulfate oxidation degradable organic pollutant The degradation effect of other pollutants is as shown in Fig. 2 in water body, and as can be seen from the figure sulphite is strengthened cupric and was catalyzed The method of oxide sulfate degradable organic pollutant has good removal effect to a variety of emerging micropollutants.
Case 3 is embodied
Specific implementation case 3 by the pH value of water sample to be processed in step (1) be adjusted to 6,8,9,10,11 it is therein any one Value, other steps are identical with case study on implementation 1.
Case 4 is embodied
Specific implementation case 4 by the sanitary sewage in step (1) change into industrial wastewater, the surface water of contaminated object, underground water or Any one water sample such as person's landfill leachate, other steps are identical with case study on implementation 1.
Case 5 is embodied
Case 5 is embodied and changes the copper nitrate in step (2) into one of copper chloride, copper sulphate or copper nitrate, chlorination Wherein 2 kinds of mixture, other steps are identical with case study on implementation 1 for copper, copper sulphate.
Case 6 is embodied
The permonosulphuric acid potassium in step (2) is changed into permonosulphuric acid sodium, permonosulphuric acid ammonia, peroxy-disulfuric acid in specific implementation case 6 Potassium, sodium persulfate, any one or several mixtures, other steps and case study on implementation 1 in peroxy-disulfuric acid ammonia are complete It is identical.
Case 7 is embodied
Specific implementation case 7 changes the sodium sulfite in step (2) into sodium hydrogensulfite, potassium sulfite, in potassium bisulfite Any one or several mixtures, other steps are identical with case study on implementation 1.
Case 8 is embodied
The concentration of copper nitrate in step (2) is adjusted to appointing in 5 μM, 15 μM, 20 μM, 30 μM and 40 μM by specific implementation case 8 It anticipates one and is worth, other steps are identical with case study on implementation 1.
Case 9 is embodied
The ratio of cupric and sodium sulfite and permonosulphuric acid potassium in step (2) is adjusted to 1:5:10 by specific implementation case 9, and 1: 20:50,1:100:300,1:100:500, several different reaction ratios, other steps are identical with case study on implementation 1.

Claims (10)

1. a kind of method that sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant, it is characterised in that: Bivalent cupric ion is quickly reduced to univalent copper ion using the reproducibility of sulphite, cupric is promoted to be catalyzed persulfate body It is the yield of potentiometric titrations, improves the degradation efficiency to organic pollutant, is realized particular by following steps:
(1) the water sample pH value to be processed containing organic pollutant is adjusted to 6-11；
(2) a certain amount of bivalent cupric ion is added into water sample to be processed, a certain amount of permonosulphuric acid potassium solution and sulfurous is then added Acid sodium solution both can achieve effective degradation to organic contamination after being thoroughly mixed reaction 5-30 minutes.
2. a kind of sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant according to claim 1 Method, it is characterised in that above-mentioned bivalent cupric ion compound includes that copper chloride, copper nitrate, copper sulphate are one such or several Mixture, but be not limited solely to these types of cupric metal salt compound, other, which contain cupric compound, all may be used With.
3. a kind of sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant according to claim 1 Method, it is characterised in that above-mentioned sulfite compound includes sodium sulfite, sodium hydrogensulfite, potassium sulfite and potassium bisulfite One of or several mixtures.
4. a kind of sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant according to claim 1 Method, it is characterised in that above-mentioned persulfate is peroxy-monosulfate or peroxydisulfate, and peroxy-monosulfate includes: permonosulphuric acid One of potassium, permonosulphuric acid sodium, permonosulphuric acid ammonium are several；Peroxydisulfate includes: permonosulphuric acid potassium, permonosulphuric acid One of sodium, permonosulphuric acid ammonium are several.
5. a kind of sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant according to claim 1 Method, it is characterised in that it is a variety of that above-mentioned water sample to be processed can be industrial wastewater, sanitary sewage, surface water, landfill leachate etc. Different water bodys.
6. sulphite strengthens the side of cupric catalysis persulfate oxidation degradable organic pollutant according to claim 1 Method, it is characterised in that 5-40 μM of bivalent cupric ion concentration in above-mentioned water sample to be processed, bivalent cupric ion in solution: sulfurous acid Salt: the reaction molar ratio of persulfate is 1:5-100:10-500.
7. a kind of sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant according to claim 1 Method, it is characterised in that 10-20 μM of bivalent cupric ion concentration in above-mentioned water sample to be processed, bivalent cupric ion in solution: sulfurous Hydrochlorate: the reaction molar ratio of persulfate is 1:30-50:150-500.
8. a kind of sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant according to claim 1 Method, it is characterised in that water sample pH value to be processed is 6-11.
9. a kind of sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant according to claim 1 Method, it is characterised in that water sample optimal pH to be processed is 6-8.
10. a kind of sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant according to claim 1 Method, it is characterised in that pollutant can be sulfamethoxazole in emerging micropollutants, carbamazepine, oestrone, nonyl phenol, Ah It is husky to take charge of a woods, chloramphenicol, penicillin, Diclofenac, naproxen, brufen, triclosan, Ciprofloxacin, Ofloxacin, promise fluorine Star, sulfamethyldiazine, any one in sulfamethazine or several mixtures.
CN201910408639.6A 2019-05-16 2019-05-16 A kind of method that sulphite strengthens cupric catalysis persulfate oxidation degradable organic pollutant Pending CN110127834A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111153486A (en) * 2019-12-27 2020-05-15 湖南大学 Method for enhancing performance of copper ion catalysis hydrogen persulfate by using green tea extract
CN111644186A (en) * 2020-06-03 2020-09-11 中山大学 Method for removing ibuprofen by utilizing persulfate activation
CN112624298A (en) * 2020-12-29 2021-04-09 四川大学 Advanced treatment process and system for sewage
CN112811557A (en) * 2019-11-15 2021-05-18 四川大学 Water treatment method for strengthening copper-activated persulfate by utilizing zero-valent metal
CN113501562A (en) * 2021-08-03 2021-10-15 吉林建筑大学 Photodegradant of carbamazepine, method and device for degrading carbamazepine

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104876320A (en) * 2015-05-04 2015-09-02 四川大学 Method for generating hydroxyl free radicals by reacting copper-ion catalytic reducing agent with oxygen
CN107857352A (en) * 2017-11-15 2018-03-30 长沙市镇源环境工程有限公司 A kind of method for removing organic pollutants
CN109368764A (en) * 2018-12-05 2019-02-22 浙江工商大学 A kind of method for treating water for strengthening persulfate oxidation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104876320A (en) * 2015-05-04 2015-09-02 四川大学 Method for generating hydroxyl free radicals by reacting copper-ion catalytic reducing agent with oxygen
CN107857352A (en) * 2017-11-15 2018-03-30 长沙市镇源环境工程有限公司 A kind of method for removing organic pollutants
CN109368764A (en) * 2018-12-05 2019-02-22 浙江工商大学 A kind of method for treating water for strengthening persulfate oxidation

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112811557A (en) * 2019-11-15 2021-05-18 四川大学 Water treatment method for strengthening copper-activated persulfate by utilizing zero-valent metal
CN111153486A (en) * 2019-12-27 2020-05-15 湖南大学 Method for enhancing performance of copper ion catalysis hydrogen persulfate by using green tea extract
CN111644186A (en) * 2020-06-03 2020-09-11 中山大学 Method for removing ibuprofen by utilizing persulfate activation
CN112624298A (en) * 2020-12-29 2021-04-09 四川大学 Advanced treatment process and system for sewage
CN113501562A (en) * 2021-08-03 2021-10-15 吉林建筑大学 Photodegradant of carbamazepine, method and device for degrading carbamazepine

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Application publication date: 20190816