CN103787495A - Method for removing triclosan from wastewater in reduction manner by virtue of zero-valent zinc under anaerobic condition - Google Patents
Method for removing triclosan from wastewater in reduction manner by virtue of zero-valent zinc under anaerobic condition Download PDFInfo
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- CN103787495A CN103787495A CN201410027296.6A CN201410027296A CN103787495A CN 103787495 A CN103787495 A CN 103787495A CN 201410027296 A CN201410027296 A CN 201410027296A CN 103787495 A CN103787495 A CN 103787495A
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Abstract
The invention relates to a method for removing triclosan from wastewater in a reduction manner by virtue of zero-valent zinc under an anaerobic condition. The method comprises the following steps: adding 1-5g of the zero-valent zinc into 1L of the wastewater containing the triclosan with the mass concentration of 1-10mg/l under the anaerobic condition, reacting for 6-12 hours, and removing the triclosan from the wastewater in the reduction manner. Compared with the prior art, the method has the advantages that the reaction condition is simple, easy and mild, the processing time is short, the triclosan removal rate is high, no secondary pollution is caused, the harm of the triclosan-containing wastewater on an environment is reduced, and the recycling of the subsequent wastewater is facilitated.
Description
Technical field
The present invention relates to a kind of sewage water treatment method containing triclosan, especially relate to and under a kind of anaerobic condition, utilize zeroth order zinc to method that in sewage, triclosan reduction is removed.
Background technology
Medicine and Personal hygiene nursing materials (Pharmaceuticals and personal care products, PPCPs) be the ubiquitous organic micro-pollutant in water and sewage of finding after Insecticides (tech) & Herbicides (tech) and endocrine disrupter, its impact that environment is caused has caused extensive concern both domestic and external.Once PPCPs enters in human body, will be transformed into polarity, deliquescent meta-bolites and acid, along with urine and ight soil enter in municipal effluent.Research shows, traditional biological process is difficult to remove completely all PPCPs.Therefore, after Sewage Plant is processed, residual PPCPs can enter in surface water, underground water or seawater along with the discharge of Sewage Plant tail water, thereby the mankind are exerted an influence and aquatic environment is damaged.
In the past few decades, existence and the removal situation of foreign study person to PPCPs in Sewage Plant entered a large amount of investigation.The people such as Gracia-Lor have investigated existence and the removal situation of 50 kinds of target P PCPs in three sewage works of Spain, it is residual that they have detected 17 kinds of PPCPs in sewage effluents, is mainly anodyne class, antiphlogistic drug class, antibiotics, hypolipidemic class, anti-allergy agent similar drug.Previous research is found, antiphlogistic drug, microbiotic, diuretic(s), hypolipidemic, anti-allergy agent, stimulants are the drug contamination things extensively existing in the water inlet of Sewage Plant abroad, due to difference and the sewage source difference of selected target PPCPs, its concentration range can be from hundreds of pg/L to hundreds of μ g/L.With respect to the investigation of drug contamination thing, also relatively less to the investigation of Personal hygiene nursing materials, only mainly chlorinated organics several frequently seen in Personal hygiene nursing materials is studied to (wherein triclosan and triclocarban are the Personal hygiene nursing materialss being often detected), because chlorinated organics is widely used in sanitas, opalizer, sterilant and sterilizing agent etc. in Personal hygiene nursing materials.Chlorinated organics can cause great harm to HUMAN HEALTH and environment, and chlorinated organics has carinogenicity, teratogenecity and mutagenicity conventionally, and is difficult to be removed completely by biology.Triclosan, as a kind of wide-spectrum bactericide, is widely used among the household chemicals such as soap, toothpaste, finds its ubiquity in the water inlet of Sewage Plant in investigation.The people such as Bendz, the people such as Yu, the people such as people and Lishman such as G ó mez investigate triclosan in Sewage Plant, and they find that the clearance of triclosan is different in Sewage Plant, are respectively 58%, 69%, 88% and 93%.In the U.S., 84% the soap with germ resistance all contains triclosan, and its consumption is up to 1500 tons/year.Triclosan has been used 50 years as high yield chemical substance nearly in the U.S., but until its harm in recent years just causes that people pay close attention to.
Find that by the previously existence to typical PPCPs in Sewage Plant and removal condition survey research traditional biological process is poor to the removal effect of chloride PPCPs, and its removal effect is subject to the impact of influent quality and Sewage Plant treatment process.In recent years, there are some researches show that zeroth order zinc and Zero-valent Iron have reduction dechlorination to chlorinated organics, can have good removal effect to chlorinated organics.Wherein the research of Zero-valent Iron is mainly concentrated on to nano zero valence iron, Zhang etc. find while utilizing nano zero valence iron degraded trichoroacetic acid(TCA), trieline and zellon, and their clearances in 24 hours can reach 99%.The people's such as Lowry research shows, the dechlorination effect of nano zero valence iron will be much better than micron order Zero-valent Iron, and nano zero valence iron can be the chlordiphenyl that toxicity is lower by polychlorobiphenyl dechlorination.Although nano zero valence iron has a lot of advantages, in the process of its application, also run into some problems, such as the less stable of nano zero valence iron.Have and report that nano zero valence iron is easy to oxidized and forms the oxide compound of iron or oxyhydroxide at Nanoscale Iron surface deposition, thereby make nano zero valence iron produce passivation.But the research that utilizes zeroth order zinc to remove chlorinated organics is relatively less, especially under anaerobic, because under anaerobic can avoid the oxygenizement of oxygen to metal, make active metal better to the removal effect of chlorinated organics.Therefore, be necessary to carry out corresponding research work.
Summary of the invention
Object of the present invention be exactly provide in order to overcome the defect that above-mentioned prior art exists that a kind of reaction conditions is simple, reaction temperature and, utilize under the anaerobic condition of short, high to the clearance of triclosan, non-secondary pollution for the treatment of time zeroth order zinc to method that in sewage, triclosan reduction is removed.The method can be removed the triclosan in sewage quickly and efficiently, reduces containing the harm of triclosan sewage to environment, is conducive to the recycling of follow-up sewage.
Object of the present invention can be achieved through the following technical solutions:
A method of utilizing zeroth order zinc to remove triclosan reduction in sewage under anaerobic condition, under anaerobic, in the sewage that contains triclosan, adds zeroth order zinc, reaction times 6-12 hour, and temperature of reaction is not limit, and the triclosan in sewage is reduced to removal.
The mechanism of utilizing zeroth order zinc to remove the reduction of triclosan under anaerobic condition is: under anaerobic, the zeroth order zinc generation hydrogen ion that is corroded in the aqueous solution, due to the difference of pH, the hydrogen ion concentration producing is also different, and the hydrogen ion of high density can aggravate the corrosion of zeroth order zinc, make triclosan generation reduction reaction and removed.
Described anaerobic condition is to blow by pass into nitrogen in reaction unit the air of catching up with in reaction unit, and seals and realize.
In described sewage, the mass concentration of triclosan is 1～10 milligrams per liter, and the input amount of described zeroth order zinc is in every liter of sewage, to add 1～5 gram.
As preferably, the input amount of described zeroth order zinc is in every liter of sewage, to add 4 grams.
Before adding zeroth order zinc, regulating the pH value of sewage is 3～10.
As preferably, before adding zeroth order zinc, regulating the pH value of sewage is 3～7.
As further preferably, before adding zeroth order zinc, regulating the pH value of sewage is 5～7.
Compared with prior art, the present invention has the following advantages and beneficial effect:
1, applied widely, reaction conditions is simple.The present invention adds zeroth order zinc in the waste water that contains triclosan, and temperature of reaction is not limit, and under normal temperature and pressure, can reach good removal effect.
2, speed of reaction is fast.Just can be to being that the sewage of the triclosan of 1-10 milligrams per liter has good removal effect containing mass concentration in 6-12 hour.
3, processing cost is low.Zeroth order zinc is easily obtained, and expense is low, has a good application prospect.
4, environmental friendliness.The zeroth order zinc that utilizes of the present invention is removed the triclosan in sewage, and the toxicity of its degraded product significantly reduces, and is conducive to the recycling of sewage.
5, applicable target compound scope is wide.The present invention, except being applicable to the sewage containing triclosan, is also applicable to the sewage of chlorinated organics.
Accompanying drawing explanation
Fig. 1 is pH value and the impact of reaction times on triclosan clearance of sewage;
Fig. 2 is dosage and the impact of reaction times on triclosan clearance of zeroth order zinc.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The analyzing and testing of triclosan adopts Agilent7890A-5975C VL MSD gas chromatograph-mass spectrometer: chromatographic column adopting HP-5MS (30 meters × 0.25 millimeter × 0.25 micron); 270 degrees Celsius of injector temperatures; 80 degrees Celsius of starting temperatures, keep 3 minutes; Rise to 300 degrees Celsius with the speed of 20 centigrade per minutes, keep 7 minutes; Carrier gas is helium.1 milliliter of per minute of flow rate of carrier gas; Splitting ratio 10: 1, sample size 1 microlitre.Mass spectrum condition: ionization mode EI, 70 electron-volts of ionizing energies, 280 degrees Celsius of ion source temperatures.Transmission line temperature: 250 degrees Celsius, sweep limit: 41-450 atomic mass unit, mass spectrum java standard library: NIST storehouse.
Embodiment 1
Under anaerobic condition, utilize zeroth order zinc to the method that in sewage, triclosan reduction is removed, process the sewage containing 10 milligrams per liter of triclosans.
Regulating sewage initial pH value is 3, adds 2.5 grams of every liter of sewage of zeroth order zinc, within 20 minutes, blows the air of catching up with in reaction unit to guarantee strict anaerobic condition, and seal to passing into nitrogen in reaction unit, detects the clearance of triclosan in different time.
Embodiment 2
Difference from Example 1 is, regulating sewage initial pH value is 5.
Embodiment 3
Difference from Example 1 is, regulating sewage initial pH value is 7.
Embodiment 4
Difference from Example 1 is, regulating sewage initial pH value is 9.
Embodiment 5
Difference from Example 1 is, regulating sewage initial pH value is 10.
In embodiment 1～5, when each embodiment carries out, in the time of the differential responses time (1,3,5,7,9,11,12 hour), detect sewage in the clearance of triclosan, result is as shown in Figure 1.As seen from Figure 1, pH, within the scope of 3-7, reacts after 12 hours, the clearance of triclosan is greater than 93%, and along with pH continues to raise, the clearance of triclosan declines gradually, therefore in order to make triclosan have good removal effect, pH is controlled at acid to neutral best.
Embodiment 6
Under anaerobic condition, utilize zeroth order zinc to the method that in sewage, triclosan reduction is removed, process the sewage containing 10 milligrams per liter of triclosans.
Regulating sewage initial pH value is 7, adds 1 gram of every liter of sewage of zeroth order zinc, within 20 minutes, blows the air of catching up with in reaction unit to guarantee strict anaerobic condition, and seal to passing into nitrogen in reaction unit, detects the clearance of triclosan in different time.
Embodiment 7
Difference from Example 6 is, adds 2 grams of every liter of sewage of zeroth order zinc.
Embodiment 8
Difference from Example 6 is, adds 2.5 grams of every liter of sewage of zeroth order zinc.
Embodiment 9
Difference from Example 6 is, adds 4 grams of every liter of sewage of zeroth order zinc.
Embodiment 10
Difference from Example 6 is, adds 5 grams of every liter of sewage of zeroth order zinc.
In embodiment 6～10, when each embodiment carries out, in the time of the differential responses time (1,3,5,7,9,11,12 hour), detect sewage in the clearance of triclosan, result is as shown in Figure 2.As seen from Figure 2, along with the increase gradually of zeroth order zinc dosage, in sewage, the clearance of triclosan improves gradually, especially in the time that the dosage of zeroth order zinc is increased to 4 grams every liter from 1 gram every liter, and continuation increases the dosage of zeroth order zinc, the removal effect of triclosan increases not obvious, therefore the suggestion of best zeroth order zinc dosage is controlled at 4 grams every liter.
Embodiment 11
Under a kind of anaerobic condition, utilize the method for zeroth order zinc to triclosan reduction removal in sewage, regulating sewage initial pH value is 7, in the sewage that contains triclosan, add zeroth order zinc, in sewage, the mass concentration of triclosan is 10 milligrams per liter, the input amount of zeroth order zinc is in every liter of sewage, to add 5 grams, within 20 minutes, blow the air of catching up with in reaction unit to passing into nitrogen in reaction unit, and seal 12 hours reaction times, temperature of reaction is not limit, and the triclosan in sewage is reduced to removal.
Embodiment 12
Under a kind of anaerobic condition, utilize the method for zeroth order zinc to triclosan reduction removal in sewage, regulating sewage initial pH value is 7, in the sewage that contains triclosan, add zeroth order zinc, in sewage, the mass concentration of triclosan is 1 milligrams per liter, the input amount of zeroth order zinc is in every liter of sewage, to add 1 gram, within 20 minutes, blow the air of catching up with in reaction unit to passing into nitrogen in reaction unit, and seal 6 hours reaction times, temperature of reaction is not limit, and the triclosan in sewage is reduced to removal.
Claims (7)
1. a method of utilizing zeroth order zinc to remove triclosan reduction in sewage under anaerobic condition, is characterized in that, under anaerobic, in the sewage that contains triclosan, adds zeroth order zinc, and reaction times 6-12 hour reduces removal to the triclosan in sewage.
2. under a kind of anaerobic condition according to claim 1, utilize the method for zeroth order zinc to triclosan reduction removal in sewage, it is characterized in that, described anaerobic condition is to blow by pass into nitrogen in reaction unit the air of catching up with in reaction unit, and seals and realize.
3. under a kind of anaerobic condition according to claim 1, utilize the method for zeroth order zinc to triclosan reduction removal in sewage, it is characterized in that, in described sewage, the mass concentration of triclosan is 1～10 milligrams per liter, and the input amount of described zeroth order zinc is in every liter of sewage, to add 1～5 gram.
4. under a kind of anaerobic condition according to claim 3, utilize zeroth order zinc to the method that in sewage, triclosan reduction is removed, it is characterized in that, the input amount of described zeroth order zinc is in every liter of sewage, to add 4 grams.
5. under a kind of anaerobic condition according to claim 1, utilize zeroth order zinc to the method that in sewage, triclosan reduction is removed, it is characterized in that, before adding zeroth order zinc, regulating the pH value of sewage is 3～10.
6. under a kind of anaerobic condition according to claim 5, utilize zeroth order zinc to the method that in sewage, triclosan reduction is removed, it is characterized in that, before adding zeroth order zinc, regulating the pH value of sewage is 3～7.
7. under a kind of anaerobic condition according to claim 6, utilize zeroth order zinc to the method that in sewage, triclosan reduction is removed, it is characterized in that, before adding zeroth order zinc, regulating the pH value of sewage is 5～7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110845004A (en) * | 2019-11-22 | 2020-02-28 | 北京工业大学 | Method for enhancing biological degradation of triclosan in nitration system by using surfactant |
| CN111453876A (en) * | 2020-02-28 | 2020-07-28 | 浙江工业大学 | Water treatment method for adsorbing tetracycline in water by using zero-valent zinc |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845004A (en) * | 2019-11-22 | 2020-02-28 | 北京工业大学 | Method for enhancing biological degradation of triclosan in nitration system by using surfactant |
| CN110845004B (en) * | 2019-11-22 | 2022-01-28 | 北京工业大学 | Method for enhancing biological degradation of triclosan in nitration system by using surfactant |
| CN111453876A (en) * | 2020-02-28 | 2020-07-28 | 浙江工业大学 | Water treatment method for adsorbing tetracycline in water by using zero-valent zinc |
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Application publication date: 20140514 |