CN102583673A - 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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- CN102583673A CN102583673A CN2012100451651A CN201210045165A CN102583673A CN 102583673 A CN102583673 A CN 102583673A CN 2012100451651 A CN2012100451651 A CN 2012100451651A CN 201210045165 A CN201210045165 A CN 201210045165A CN 102583673 A CN102583673 A CN 102583673A
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- glyphosate
- smectite
- ipa salt
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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 is 2-10g/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 smectite that utilizes combines ferric method to remove the method that Glyphosate 62 IPA Salt pollutes in the water body.
Background technology
Glyphosate 62 IPA Salt (glyphosate) is to reach the main active ingredient in (Roundup) by the weedicide farming that U.S. Monsanto Company develops.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 very soon in 1974.In recent years, because the expansion of genetically modified crops plantation, and 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 62 IPA Salt patent expire; This moment, China enterprise relied on own technological fast development, and 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 maximum in the world at present glyphosate production and export State.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 62 IPA Salt is distributed in more.
U.S. EPA classifies as Level III toxin with Glyphosate 62 IPA Salt, and many researchs show that also Glyphosate 62 IPA Salt is to the environment hazardous property.Glyphosate 62 IPA Salt can suppress ray fungi and bacterial respiratory and its living weight 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 can a large amount of Glyphosate 62 IPA Salts be entered among the environment producing, transport, use link, except that toxicity own, Glyphosate 62 IPA Salt decomposes releases phosphorus, causes body eutrophication.
In the face of the growing environmental exposure of Glyphosate 62 IPA Salt; Correlative study concentrates on its environmental behaviour; And less to trade effluent and polluted-water processing research, Glyphosate 62 IPA Salt trade effluent concentration is high usually, and salinity is high; Ordinary method is separated purification difficult, can't directly realize the recycling of Glyphosate 62 IPA Salt in the mother liquor waste water.And main at present research has photocatalytic oxidation, oxychlorination, electrode electricity solution, materialization-biochemistry combined method etc.These method existence need external energy, and treatment rate waits the technology limitation slowly.The Glyphosate 62 IPA Salt that contains higher concentration in the waste water, absorption method are the effective ways that a kind of potential is handled waste water, recovery Glyphosate 62 IPA Salt.
Discover Fe
3+Saturated soil has higher absorption (Sprankle et al 1975) to Glyphosate 62 IPA Salt.Smectite is a kind of environmental friendliness type material, and absorption property preferably, abundant raw material sources, less cost are arranged.The present invention then adopts smectite to add iron ion it is removed this research mainly through system experimentation research smectite-Fe
3+System is to the removal process of Glyphosate 62 IPA Salt 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 62 IPA Salt, 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 62 IPA Salt adsorptive capacity to the present invention is directed to simple smectite, utilize ferric iron can with the characteristic of the strong complexing of Glyphosate 62 IPA Salt, provide a kind of with low cost, gather convenient, the simple water body Glyphosate 62 IPA Salt of technology removal method.
Technical scheme:Technical scheme of the present invention is: smectite is removed the method for Glyphosate 62 IPA Salt in the waste water; Comprise following steps: smectite 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 smectite dosage 2 ~ 10g/L wherein, trivalent iron salt dosage 0.3 ~ 1 g/L.
It is≤100 orders that above-mentioned smectite 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 smectite: 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 62 IPA Salt, and ferric iron and Glyphosate 62 IPA Salt are captured the interlayer that gets into smectite.Filter or spinning the water body after can being purified then.
Beneficial effect:The present invention is raw material with natural mineral smectite and ferric iron, and is with low cost, and environmental friendliness, processing condition are very simple, mixes through simple solid-liquid, and flow processs such as solid-liquid separation can reach the effect that Glyphosate 62 IPA Salt 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.High to water body Glyphosate 62 IPA Salt adsorption efficiency, 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 smectite-Fe under the different initial pH
3+Method is to the removal effect of Glyphosate 62 IPA Salt.
Fig. 2 is different time smectite-Fe
3+Method is to the removal effect of Glyphosate 62 IPA Salt.
Fig. 3 is different Fe
3+Smectite-Fe under the dosage
3+Method is to the removal effect of Glyphosate 62 IPA Salt.
Fig. 4 is smectite-Fe under the different N aCl concentration
3+Method is to the removal effect of Glyphosate 62 IPA Salt.
Fig. 5 is smectite-Fe under the different initial Glyphosate 62 IPA Salt concentration
3+Method is to the adsorptive capacity of Glyphosate 62 IPA Salt.
Fig. 6 be Glyphosate 62 IPA Salt with etc. the removal effect of volumetric molar concentration orthophosphoric acid salt under different pH
Embodiment
The foregoing description only is used for that 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:
Smectite 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.With dosage is that 2 g/L are added to that to contain Glyphosate 62 IPA Salt be 350 mg/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 62 IPA Salt 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 pH is little to the clearance influence of Glyphosate 62 IPA Salt in the water body basically, if but initial pH reaches 12, and then this method almost loses effect to Glyphosate 62 IPA Salt, and clearance falls sharply to 3.51%.
Embodiment 2:
Smectite is purchased in the Inner Mongol, is ca-montmorillonite, purity 95%, and CEC 115-139mmo1/100g, grinding particle diameter is≤100 orders.With dosage is that 2 g/L are added to that to contain Glyphosate 62 IPA Salt be 350 mg/L, in the aqueous solution of pH 2.95 (natural pH), adds 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 62 IPA Salt 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:
Smectite is purchased in the Inner Mongol, is ca-montmorillonite, purity 95%, and CEC 115-139mmo1/100g, grinding particle diameter is≤100 orders.With dosage is that 2 g/L are added to that to contain Glyphosate 62 IPA Salt be 350 mg/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 62 IPA Salt 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%.
Can find out FeCl
36H
2The add-on of O is a controlled factor, FeCl
36H
2The add-on of O is that the removal amount with Glyphosate 62 IPA Salt is a linear relationship, and this is by removing the mechanism decision, in using, can regulating FeCl
36H
2The add-on of O adapts to practical situation and reaches best removal effect.
Embodiment 4:
Smectite is purchased in the Inner Mongol, is ca-montmorillonite, purity 95%, and CEC 115-139mmo1/100g, grinding particle diameter is≤100 orders.With dosage is that 2 g/L are added to that to contain Glyphosate 62 IPA Salt be 350 mg/L, and 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 62 IPA Salt 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%.
Can find out and find salinity to system influence of the present invention not quite, even concentration reaches 1.00 mol/L, this system does not still have any obvious variation to the clearance of Glyphosate 62 IPA Salt.So present method is applicable to the high salinity system.
Embodiment 5:
Smectite is purchased in the Inner Mongol, is ca-montmorillonite, purity 95%, and CEC 115-139mmo1/100g, grinding particle diameter is≤100 orders.With dosage is that 2 g/L are added to that to contain Glyphosate 62 IPA Salt be 250 mg/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 adsorptive capacity of Glyphosate 62 IPA Salt is 124.28 mg/g under this kind state.Under the similarity condition, initial Glyphosate 62 IPA Salt 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.
Can find out that the Glyphosate 62 IPA Salt adsorptive capacity raises and raises along with starting point concentration, reach capacity in the time of still to 500 mg/L.This characteristic has very high directive significance to the practical application of present method.
Embodiment 6:
Smectite is purchased in the Inner Mongol, is ca-montmorillonite, purity 95%, and CEC 115-139mmo1/100g, grinding particle diameter is≤100 orders.With dosage is that 2 g/L are added to that to contain Glyphosate 62 IPA Salt be 350 mg/L, and 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 62 IPA Salt 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 62 IPA Salt 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%.
Can find out that orthophosphoric acid salt has certain influence to the removal of Glyphosate 62 IPA Salt, in the practice process, can consider the method that substep is removed.
Claims (5)
1. smectite is removed the method for Glyphosate 62 IPA Salt in the water body; It is characterized in that comprising following steps: smectite 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 smectite dosage 2 ~ 10g/L wherein, trivalent iron salt dosage 0.3 ~ 1 g/L.
2. smectite according to claim 1 is removed the method for Glyphosate 62 IPA Salt in the water body, it is characterized in that it is≤100 orders that smectite is ground particle diameter.
3. smectite according to claim 1 is removed the method for Glyphosate 62 IPA Salt in the water body, it is characterized in that the method for solid-liquid separation is centrifugal or filters.
4. smectite according to claim 1 is removed the method for Glyphosate 62 IPA Salt in the water body, it is characterized in that said trivalent iron salt is FeCl
36H
2O, mixed smectite: 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 ℃.
5. smectite according to claim 1 is removed the method for Glyphosate 62 IPA Salt in the water body, it is characterized in that the orthophosphoric acid salt concentration in the glyphosate waste water is no more than 65ppm with phosphorus calculating.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277249A (en) * | 2016-08-29 | 2017-01-04 | 南京工业大学 | A kind of method removing waste water glyphosate |
| CN109603885A (en) * | 2019-01-09 | 2019-04-12 | 天津大学 | A kind of method that light assists monatomic catalytic degradation water body glyphosate |
| WO2021208305A1 (en) * | 2020-04-14 | 2021-10-21 | 南京融众环境工程研究院有限公司 | Method for removing prosulfuron in water 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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Patent Citations (3)
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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 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277249A (en) * | 2016-08-29 | 2017-01-04 | 南京工业大学 | A kind of method removing waste water glyphosate |
| CN109603885A (en) * | 2019-01-09 | 2019-04-12 | 天津大学 | A kind of method that light assists monatomic catalytic degradation water body glyphosate |
| WO2021208305A1 (en) * | 2020-04-14 | 2021-10-21 | 南京融众环境工程研究院有限公司 | Method for removing prosulfuron in water by using montmorillonite adsorbent |
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