CN102583673B - Method for removing glyphosate in water body by using montmorillonite - Google Patents
Method for removing glyphosate in water body by using montmorillonite Download PDFInfo
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- CN102583673B CN102583673B CN2012100451651A CN201210045165A CN102583673B CN 102583673 B CN102583673 B CN 102583673B CN 2012100451651 A CN2012100451651 A CN 2012100451651A CN 201210045165 A CN201210045165 A CN 201210045165A CN 102583673 B CN102583673 B CN 102583673B
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Abstract
The invention discloses a method for removing glyphosate in water body by using montmorillonite. The method comprises the following steps: grinding and drying montmorillonite, then adding glyphosate wastewater and a ferric salt, mixing evenly, performing solid-liquid separation at the reaction end point when the pH value is 2-4 and finishing the treatment, wherein the dosage of montmorillonite is2-10g/L and the dosage of the ferric salt is 0.3-1g/L. The method disclosed by the invention uses cheap raw material-montmorillonite and ferric chloride and can quickly realize the treatment of the glyphosate wastewater.
Description
Technical field
The water that the invention belongs in the environmental protection field pollutes treatment technology, and particularly a kind of montmorillonite that utilizes is removed the method that glyphosate pollutes in the water body in conjunction with ferric method.
Background technology
Glyphosate (glyphosate) is that weedicide farming by U.S. Monsanto Company exploitation reaches the main active ingredient in (Roundup).Because the characteristic of its high-efficiency broad spectrum low toxicity, become the weedicide of sales volume first after making this product come into operation in 1974 very soon.In recent years, because the expansion of genetically modified crops plantation, and the recovery of the agricultural of developing country and modernization development, the market requirement increases rapidly.1994, whole world glyphosate technicals usage quantity was at 42 500 t, and after this 3 years, increased by 20% every year approximately, nineteen ninety-five whole world consumption 67 000 t, about 74 050 t in 1997, about 112 000 t in 1998.To Meng Shan in 2001 all the glyphosate patent expire, this moment, China enterprise relied on own technology fast development, production capacity is advanced by leaps and bounds, to about 1,200,000 tons of global production capacity in 2011, so far, the glyphosate technicals manufacturing enterprise of China surpasses 49 families, and aggregated capacity reaches 720,000 tons, is present glyphosate production and the export State of maximum in the world.The density of population such as Jiangsu, Zhejiang are big, environmental capacity is little and be positioned at important basins such as the Changjiang river, Taihu Lake and the main manufacturing enterprise of China's glyphosate is distributed in more.
U.S. EPA classifies as Level III toxin with glyphosate, and many researchs show that also glyphosate is to the environment hazardous property.Glyphosate can suppress ray fungi and bacterial respiratory and its biomass is caused remarkably influenced, and the fish gill and liver are had toxic action (Roslycky et al 1982; Zhou Ding builds 2010; Neskovic et al 1996).
As a kind of organophosphorus pesticide, all a large amount of glyphosates can be entered among the environment producing, transport, use link, except toxicity own, glyphosate decomposes will discharge phosphorus, cause body eutrophication.
In the face of the growing environmental risk of glyphosate, correlative study concentrates on its environmental behaviour, and it is less at trade effluent and polluted-water processing research, common glyphosate trade effluent concentration height, the salinity height, ordinary method is separated purification difficult, can't directly realize the recycling of glyphosate in the mother liquor waste water.And main research has photocatalytic oxidation, oxychlorination, electrolysis method, materialization-biochemistry combined method etc. at present.These methods exist needs external energy, treatment rate to wait the technology limitation slowly.The glyphosate that contains higher concentration in the waste water, absorption method are a kind of potential processing waste water, the effective ways of recovery glyphosate.
Discover Fe
3+Saturated soil has higher absorption (Sprankle et al 1975) to glyphosate.Montmorillonite is a kind of environmentally friendly material, and absorption property, abundant raw material sources, cheap cost are preferably arranged.The present invention then adopts montmorillonite to add iron ion it is removed this research mainly by system experimentation research montmorillonite-Fe
3+System is to the removal process of glyphosate in the water body.To reaction times, Fe
3+A plurality of condition effect such as dosage, pH are studied, and optimize and remove efficient, investigate its application conditions, application potential and prospect.And the removal mechanism of discussion glyphosate, seek improved possibility.For a new method is sought in the processing of high salt high density glyphosate waste water.
Summary of the invention
The technical problem that solves:It is low to the glyphosate adsorptive capacity to the present invention is directed to simple montmorillonite, utilize ferric iron can with the characteristic of the strong complexing of glyphosate, provide a kind of with low cost, gather convenient, the simple water body glyphosate of technology removal method.
Technical scheme:Technical solution of the present invention is: montmorillonite is removed the method for glyphosate in the waste water, comprise following steps: montmorillonite is ground oven dry, add glyphosate waste water and trivalent iron salt then, mix, after reaching 2 ~ 4, reaction end pH carries out solid-liquid separation, finish dealing with montmorillonite dosage 2 ~ 10g/L wherein, trivalent iron salt dosage 0.3 ~ 1 g/L.
It is≤100 orders that above-mentioned montmorillonite grinds particle diameter.
The method of above-mentioned solid-liquid separation is centrifugal or filters.
Above-mentioned trivalent iron salt is FeCl
36H
2O, mixed montmorillonite: FeCl
36H
2O: the glyphosate waste water mass ratio is 10:3:5000, and the glyphosate waste water concentration of suitable treatment is 10 ~ 350mg/L, and suitable initial glyphosate waste water pH is 2 ~ 10, and optimal temperature is 25 ~ 45 ℃, and suitable hunting speed is 100 r/min, suitable reaction times＞5min.
Orthophosphoric acid salt concentration in the above-mentioned glyphosate waste water is calculated with phosphorus and is no more than 65ppm, otherwise will reduce the removal effect more than 20%.
The present invention utilizes the strong complexing action of ferric iron and glyphosate, and ferric iron and glyphosate are captured the interlayer that enters montmorillonite.Filter or centrifugation the water body after can being purified then.
Beneficial effect:The present invention is raw material with natural mineral montmorillonite and ferric iron, and is with low cost, and environmental friendliness, processing condition are very simple, mixes by simple solid-liquid, and flow processs such as solid-liquid separation can reach the effect that glyphosate is removed, and need not extra energy input.And be swift in response, in less than 5 minutes reaction times, just can reach good effect of removing.To water body glyphosate adsorption efficiency height, can under high salinity, react, it is wide to use the pH scope, can not produce murder by poisoning etc. to water body and hydrobiont.
Description of drawings:
Fig. 1 is montmorillonite-Fe under the different initial pH
3+Method is to the removal effect of glyphosate.
Fig. 2 is different time montmorillonite-Fe
3+Method is to the removal effect of glyphosate.
Fig. 3 is different Fe
3+Montmorillonite-Fe under the dosage
3+Method is to the removal effect of glyphosate.
Fig. 4 is montmorillonite-Fe under the different N aCl concentration
3+Method is to the removal effect of glyphosate.
Fig. 5 is montmorillonite-Fe under the different initial glyphosate concentration
3+Method is to the adsorptive capacity of glyphosate.
Fig. 6 be glyphosate with etc. the removal effect of volumetric molar concentration orthophosphoric acid salt under different pH
Embodiment
Above-described embodiment only for the present invention will be described, does not constitute the restriction to the claim scope, and other alternative means that it may occur to persons skilled in the art that are all in claim scope of the present invention.
Embodiment 1:
Montmorillonite is purchased in the Inner Mongol, is ca-montmorillonite, purity 95%, and cation exchange capacity (CEC) 115-139mmo1/100g, grinding particle diameter is≤100 orders.Be that 2 g/L are added to that to contain glyphosate be 350 mg/L with dosage, in the aqueous solution of pH 2.95, add FeCl
36H
2In 25 ℃ of vibrations down, duration of oscillation is 2 hours to O to 0.6 g/L with 100 r/min.The result shows that the clearance of glyphosate is 96.67% under this kind state.Under the similarity condition, the initial pH of solution makes initial pH be respectively 2,4,6,8,10,12 with HCl and the NaOH adjusting of 0.1 mol/L, and corresponding clearance is respectively 95.76%, 97.32%, 98.05%, 98.05%, 96.29%, 3.51%.
Hence one can see that in initial pH2 ~ 10, and the influence of the clearance of glyphosate is little in the water body of pH basically, if but initial pH reaches 12, and then this method almost loses effect to glyphosate, and clearance falls sharply to 3.51%.
Embodiment 2:
Montmorillonite is purchased in the Inner Mongol, is ca-montmorillonite, purity 95%, and CEC 115-139mmo1/100g, grinding particle diameter is≤100 orders.Be that 2 g/L are added to that to contain glyphosate be 350 mg/L with dosage, in the aqueous solution of pH 2.95 (natural pH), add FeCl
36H
225 ℃ of vibrations down, duration of oscillation is 5min to O to 0.6 g/L with 100 r/min.The result shows that the clearance of glyphosate is 92.51% under this kind state.Under the similarity condition, duration of oscillation changes 10,20,40,60,90 into, 120min, and corresponding clearance is respectively 92.62%, 91.96%, 92.60%, 95.72%, 98.02%, 97.24%.
Hence one can see that reaches balance in being reflected at 5min, very fast, is easy to the actual waste water application in engineering.
Embodiment 3:
Montmorillonite is purchased in the Inner Mongol, is ca-montmorillonite, purity 95%, and CEC 115-139mmo1/100g, grinding particle diameter is≤100 orders.Be that 2 g/L are added to that to contain glyphosate be 350 mg/L with dosage, in the aqueous solution of pH 2.95, add FeCl
36H
2In 25 ℃ of vibrations down, duration of oscillation is 2 hours to O to 0.6 g/L with 100 r/min.The result shows that the clearance of glyphosate is 96.67% under this kind state.Under the similarity condition, the FeCl of adding
36H
2The O amount is adjusted to 0.05,0.10,0.16,0.20,0.40,1.30,2 g/L, and corresponding clearance is respectively 12.26%, 14.74%, 22.82%, 43.78%, 74.28%, 95.94%, 95.47%.
FeCl as can be seen
36H
2The add-on of O is a controlled factor, FeCl
36H
2The add-on of O is that the removal amount with glyphosate is a linear relationship, and this is to determine by removing mechanism, can regulate FeCl in using
36H
2The add-on of O adapts to practical situation and reaches best removal effect.
Embodiment 4:
Montmorillonite is purchased in the Inner Mongol, is ca-montmorillonite, purity 95%, and CEC 115-139mmo1/100g, grinding particle diameter is≤100 orders.Be that 2 g/L are added to that to contain glyphosate be 350 mg/L with dosage, NaCl is 0.01 mol/L, in the aqueous solution of pH 2.95, adds FeCl
36H
2In 25 ℃ of vibrations down, duration of oscillation is 2 hours to O to 0.6 g/L with 100 r/min.The result shows that the clearance of glyphosate is 96.28% under this kind state.Under the similarity condition, initial NaCl concentration adjustment becomes 0.05,0.10,0.50,1.00 mol/L, and corresponding clearance is respectively 97.17%, 96.70%, 96.82%, 97.49%.
Find that as can be seen salinity is little to system influence of the present invention, even concentration reaches 1.00 mol/L, this system does not still have any obvious variation to the clearance of glyphosate.So present method is applicable to the high salinity system.
Embodiment 5:
Montmorillonite is purchased in the Inner Mongol, is ca-montmorillonite, purity 95%, and CEC 115-139mmo1/100g, grinding particle diameter is≤100 orders.Be that 2 g/L are added to that to contain glyphosate be 250 mg/L with dosage, in the aqueous solution of pH 2.95, add FeCl
36H
2In 25 ℃ of vibrations down, duration of oscillation is 2 hours to O to 0.6 g/L with 100 r/min.The result shows that the adsorptive capacity of glyphosate is 124.28 mg/g under this kind state.Under the similarity condition, initial glyphosate concentration adjustment becomes 350,400,450,500,600 mg/L, and corresponding adsorptive capacity is respectively 170.32,186.62,196.41,212.52,209.80.
As can be seen, the glyphosate adsorptive capacity raises and raises along with starting point concentration, reaches capacity in the time of still to 500 mg/L.This characteristic has very high directive significance to the application in practice of present method.
Embodiment 6:
Montmorillonite is purchased in the Inner Mongol, is ca-montmorillonite, purity 95%, and CEC 115-139mmo1/100g, grinding particle diameter is≤100 orders.Be that 2 g/L are added to that to contain glyphosate be 350 mg/L with dosage, potassium primary phosphate 282mg/L (calculating with phosphorus 65ppm) in the aqueous solution of pH 4.0, adds FeCl
36H
2In 25 ℃ of vibrations down, duration of oscillation is 2 hours to O to 0.6 g/L with 100 r/min.The result shows that the clearance of glyphosate is 79.83% under this kind state, and the orthophosphoric acid salt clearance is 45.75%.Under the similarity condition, initial pH saves into 2,6,8,10,11,12, corresponding glyphosate clearance is respectively 74.05%, 77.77%, 71.56%, 54.81%, 40.22%, 28.73%, and corresponding orthophosphoric acid salt clearance is 36.55%, 48.73%, 44.62%, 35.00%, 30.62%, 33.57%.
Orthophosphoric acid salt has certain influence to the removal of glyphosate as can be seen, can consider the method that substep is removed in the practice process.
Claims (1)
1. montmorillonite is removed the method for glyphosate in the waste water, it is characterized in that comprising following steps: montmorillonite is ca-montmorillonite, purity 95%, cation exchange capacity 115-139mmo1/100g, grinding particle diameter is≤100 orders, is that 2 g/L are added to that to contain glyphosate be 350 mg/L with montmorillonite dosage, potassium primary phosphate 282mg/L, in the aqueous solution of pH 4.0, add FeCl
36H
2In 25 ℃ of vibrations down, duration of oscillation is 2 hours to O to 0.6 g/L with 100 r/min.
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| CN106277249A (en) * | 2016-08-29 | 2017-01-04 | 南京工业大学 | Method for removing glyphosate in wastewater |
| CN109603885B (en) * | 2019-01-09 | 2020-12-11 | 天津大学 | Method for degrading glyphosate in water body by photo-assisted monatomic catalysis |
| CN111362348A (en) * | 2020-04-14 | 2020-07-03 | 南京融众环境工程研究院有限公司 | Method for removing prosulfuron in water body by using montmorillonite adsorbent |
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| CN101254958A (en) * | 2008-03-25 | 2008-09-03 | 浙江华特新材料股份有限公司 | Attapulgite sewage water treating method |
| CN101659463A (en) * | 2009-09-10 | 2010-03-03 | 重庆大学 | Method for treatment of industrial phosphorus-containing wastewater |
| CN102180535A (en) * | 2011-03-25 | 2011-09-14 | 中国科学院南京土壤研究所 | Method for removing phosphorus in organophosphorus pesticide waste water by using metal compound complex mineral material |
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| CN101254958A (en) * | 2008-03-25 | 2008-09-03 | 浙江华特新材料股份有限公司 | Attapulgite sewage water treating method |
| CN101659463A (en) * | 2009-09-10 | 2010-03-03 | 重庆大学 | Method for treatment of industrial phosphorus-containing wastewater |
| CN102180535A (en) * | 2011-03-25 | 2011-09-14 | 中国科学院南京土壤研究所 | Method for removing phosphorus in organophosphorus pesticide waste water by using metal compound complex mineral material |
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