CN103523887A - Treatment method for glyphosate wastewater - Google Patents
Treatment method for glyphosate wastewater Download PDFInfo
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- CN103523887A CN103523887A CN201310460343.1A CN201310460343A CN103523887A CN 103523887 A CN103523887 A CN 103523887A CN 201310460343 A CN201310460343 A CN 201310460343A CN 103523887 A CN103523887 A CN 103523887A
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Abstract
The invention discloses a treatment method for glyphosate wastewater. The treatment method for the glyphosate wastewater comprises the following steps: weighing 1.0000 g of a 95% glyphosate, then adding 100 mL of distilled water, dissolving in a beaker, then weighing accurately aluminum chloride according to the molar ratio of glyphosate to aluminum chloride of 1:4, adding into the beaker to dissolve, then adjusting the pH of the solution to be neutral by using sodium hydroxide, and stirring for 9 hours at the temperature of 30 DEG C; filtering, drying, carrying out suction filtration of the treatment liquid by a circulating water vacuum pump, and then putting the filter cake into an electric-heating constant-temperature air blast drying box for drying; measuring the volume of the treated filtrate, carrying out nitrosation, measuring by an ultraviolet spectrophotometer, and carrying out infrared spectroscopy detection of the dried filter cake; and measuring the content of organic pollutants. The recovery rate of glyphosate obtained by a metathesis reaction is high, and great contributions are made to implementation of energy-saving emission reduction and to realization of social economic sustainable development. In addition, the method disclosed by the invention is simple, effectively treats the glyphosate wastewater, and protects the environment.
Description
Technical field
The invention belongs to technical field of waste water processing, relate in particular to a kind for the treatment of process of glyphosate waste water.
Background technology
At present, glyphosate production wastewater is a kind of acid waste water containing high density inorganic salt and high-enriched organics, wherein pollutent mainly contains methyl alcohol, formaldehyde, glyphosate, COD mass concentration is in 48000-52000mg/L left and right, the inorganic salt that also contain 15% left and right, as sodium-chlor (NaCl), therefore, at present the most of manufacturing enterprises of China are by being that 10% gyphosate solution is sold to adding a certain amount of glyphosate dry powder and auxiliary agent to make massfraction after this Waste water concentrating, but like this, inorganic salt and organism a large amount of in waste water are brought in farmland, will further cause soil compaction and salinization, and the pollution of water body, so lot of domestic and foreign scientific research personnel has carried out a large amount of research work for this reason, the main physico-chemical processes that adopts, biological treatment, the glyphosate waste water treatment technologies such as combination process method.
The treatment process of glyphosate production wastewater comprises hydrolysis method, biochemical process, chemical precipitation method, chemical oxidization method, active carbon adsorption, resin adsorption method, advanced oxidation processes, combination treatment method, membrane sepn;
(1) chemical precipitation method
Xu Mingli etc. have studied pre-treatment and the comprehensive utilization of glyphosate production wastewater, first with CaC12 solution, as precipitation agent, make glyphosate generate calcium precipitation, precipitation processes by tenderizer that to obtain massfraction be 5% the glyphosate aqueous solution, in this technique, the rate of recovery of glyphosate reaches 95%, CODcr clearance is greater than 95%, fully realized the comprehensive utilization of glyphosate waste water, Liu Guoqing etc. are in a kind of patent of invention for the treatment of process of glyphosate waste water, glyphosate production wastewater is added in alkali and reclaim after catalyzer, add excessive calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, calcium salt or magnesium salts, fully after reaction, filter, the filter cake of the calcium salt that obtains containing glyphosate or the magnesium salts of glyphosate, by filter cake by mineral acid treatment and obtain glyphosate solution, measure the content of COD in the content of glyphosate and filtrate, show that the glyphosate rate of recovery reaches 95%, COD clearance reaches 95%, Gao Fangfang etc. are in precipitation and the processing of metathesis combined recovery glyphosate and the research of resource utilization approach, the clearance of glyphosate reaches more than 95%, when reclaiming, add appropriate Na
2cO
3, the rate of recovery that obtains glyphosate by replacement(metathesis)reaction reaches 97.8%,
(2) absorption method
Absorption method is a kind of less energy-consumption Solid phase extraction separation method, extensively paid attention to and be applied in waste water treatment process, lot of domestic and foreign scientific research personnel is just studying glyphosate and heavy metal ion on various common sorbent materials at present, adsorption mechanism and the Adsorption Model of inorganic phosphate radical ion etc., for example: activated alumina has good adsorption-desorption treatment effect to glyphosate, by 10mL A1-1 alumina adsorption, process after glyphosate waste water, the clearance of glyphosate reaches more than 98%, COD clearance reaches 50%, activated carbon supported hydrous iron oxide absorption method reaches 120mg/g to the maximum adsorption capacity of glyphosate, adsorptive capacity reduces with the rising of pH, and phosphate radical obviously suppresses the absorption property of AC-Fe, Li Changhai, Li Zhenyu, repair gorgeous China etc. and take D301R macroporous weakly basic anion exchange resin as sorbent material, result CODcr clearance reaches 96%, and can effectively remove the CLT acid in waste water, Xiao Gu waits with 330 anionite-exchange resin the Study on adsorption properties of glyphosate is found clearly, cooling is conducive to absorption, NaCl content increases, adsorption effect significantly reduces,
(3) chemical oxidization method
Chlorine oxidation process be with hydrochloric acid by glyphosate mother solution acidifying adjust pH, then add sodium chlorate solution to react to obtain dioxide peroxide, Chlorine Dioxide Oxidation glyphosate and other organism afterwards, obtaining glyphosate rate of decomposition is 70% left and right;
Hydrogen peroxide oxidation method is to use hydrogen peroxide oxidation glyphosate mother solution, and go forward side by side oxidation step glyphosate and other organism obtain small molecules or inorganics through oxidation organic macromolecule, and now glyphosate rate of decomposition reaches 40% left and right,
Also has High Temperature High Pressure catalytic oxidation, the ultraviolet oxidation style of special wavelength etc.;
(4) biochemical process
Novel anaerobic baffled reactor for Cao Xiaoying etc. (ABR) is processed glyphosate waste water, when raw wastewater CODcr mass concentration is within the scope of 6000-7000mg/L, the HRT that reactor is set is 15-18h, under mesophilic condition, after processing, the clearance of CODcr reaches 95.6%, and pollutants removal rate is up to more than 95%;
(5) advanced oxidation processes
The use Fendon reagent such as Liao Huan carry out pre-treatment glyphosate waste water, finally obtain total tp removal rate and reach 95.7%, CODcr clearance reaches 62.9%, the advantage of the method is a large amount of organic pollutants that can remove in glyphosate waste water, alleviated the pressure of follow-up biochemical treatment, Fendon photocatalysis degradation glyphosate waste water for Gu Yan etc., with sunlight and ultraviolet degradation waste water, at pH=3.0, n (H
2o
2): n (Fe
2+under the condition of)=10: 1, COD clearance is greater than in the experimental studies that useful component utilizes in glyphosate waste water such as 82%, Li Qihui, has adopted Fenton-Mg (OH)
2method is processed glyphosate waste water, first use the organism of Fenton reagent oxidation difficult degradation, with adsorption of magnesium hydroxide sedimentation, process again, can not only effectively remove organism, and COD clearance can be up to more than 76%, Fu Guanglong etc., in Fenton agent treated glyphosate waste water test, draw in pH=3, reaction times to be that 30min, temperature of reaction are under the condition of 60 ℃, add 1.0mL H
2o
2(, 30%) and 0.25gFeSO
47H
2o, the CODcr clearance of glyphosate waste water reaches 91.98%;
Dong Wengeng etc., in the research of Oxidation Pretreatment of Wastewater from Glyphosate Production with Sodium Hypochlorite, obtain in former alkaline waste water, and clorox add-on is equivalent to the available chlorine of theoretical amount 40%, under room temperature, reacts 4h, and the clearance of glyphosate can reach 98%;
(, 6) and combination treatment method
Zhang Huanzhen etc. process with selectivity organism reactor-UASB-CAAS combination process the glyphosate waste water by after electrolysis pretreatment, first by electrolysis treatment, remove chlorion, adopt again selectivity organism reactor (UASB) and up-flow anaerobic sludge blanket to remove most organic pollutant (COD), finally use Anoxic/Aerobic combined system (CAAS) to process, after processing, COD clearance reaches 99%;
Tang Jie etc. adopt multi-dimensional electro-catalytic art breading glyphosate mother solution, and COD clearance all reaches 85% left and right, and total tp removal rate reaches 90%;
(7) membrane separation concentration method
Membrane separation technique is an emerging technology in recent years, by selection through performance separating mixture, purification and the concentrated new separation technology that draws object product of film.
There is complicated operation in existing glyphosate waste water treatment process, processing cost is high, the problem that efficiency is not good.
Summary of the invention
The object of the embodiment of the present invention is to provide a kind for the treatment of process of glyphosate waste water, is intended to solve existing glyphosate waste water treatment process and has complicated operation, and processing cost is high, the problem that efficiency is not good.
The embodiment of the present invention is achieved in that a kind for the treatment of process of glyphosate waste water, and the treatment process of this glyphosate waste water comprises the following steps:
Further, in step 2, electric heating constant-temperature blowing drying box is set to 50 ℃.
Further, in step 3, the concrete grammar of glyphosate nitrosylation is:
With transfer pipet, accurately draw with the filtrate 10mL of filter filtration in 100mL volumetric flask, add successively 0.5mL sulphuric acid soln, 0.1mL potassium bromide solution, 0.5mL sodium nitrite solution, rapidly by stopper jam-pack, fully shake up, place 20min, with distilled water diluting to scale, shake up, open stopper, place 10min, nitrite acidizing temperature of reaction is greater than 15 ℃.
Further, being formulated as of sulphuric acid soln: the volume ratio of sulfuric acid and water is to be mixed with 50% sulphuric acid soln at 1: 1.
Further, being formulated as of sodium nitrite solution: take 0.28g Sodium Nitrite, be dissolved in 20mL distilled water.
Further, being formulated as of KBr solution: accurately take 25gKBr and be surely dissolved in 100mL volumetric flask.
Further, the concrete grammar of step 4 is:
The first step, gets the glyphosate waste water treatment solution of 5.00mL, is diluted to 100mL;
Second step, the water sample of getting 20.00mL dilution is placed in the backflow Erlenmeyer flask of 250mL ground, take the Mercury bisulfate of 0.4g, add 10.00mL potassium bichromate standardized solution and several little granulated glass spherees or zeolite, the spherical condensation tube that connects ground, from the prolong 30mL sulfuric acid-silver sulfate solution that adds at leisure suitable for reading, shake gently Erlenmeyer flask solution is evenly mixed, reflux 2h;
The 3rd step, cooling after, with 90mL distilled water, by prolong is suitable for reading, slowly pour into, take off Erlenmeyer flask, overall solution volume is not less than 140mL;
The 4th step, after solution is again cooling, adds 3 phenanthroline ion indicating liquids, and with the titration of ferrous ammonium sulphate standardized solution, the color of solution is terminal by yellow through blue-greenish colour to sorrel, records the consumption of ferrous ammonium sulphate standardized solution;
The 5th step, when measuring water sample, gets 20.00mL distilled water, by same operation steps, does blank test, the consumption of ferrous ammonium sulphate standardized solution when blank measured in record;
Calculation formula:
CODcr(O
2，mg/L)＝[(V
0-V1)×C×8×1000]/V
In formula: the concentration of C---ferrous ammonium sulphate standardized solution;
The consumption of ferrous ammonium sulphate standardized solution when V0---titration is blank;
The consumption of ferrous ammonium sulphate standardized solution during V1---Titration Water Sample;
The volume of V---water sample;
8---oxygen (1/2O) molar mass.
Further, being formulated as of potassium bichromate standardized solution: potassium bichromate is dried to 2h to mass conservation at 120 ℃, accurately take 3.0645g soluble in water, move into 250mL volumetric flask, be diluted to standard lines, shake up;
Being formulated as of phenanthroline ion indicating liquid: take the adjacent luxuriant and rich with fragrance sound of vomiting of 1.485g quinoline, 0.695g ferrous sulfate is soluble in water, is diluted to 100mL, be stored in brown bottle;
Being formulated as of ferrous ammonium sulphate standardized solution: take 39.5g ferrous ammonium sulphate soluble in water, slowly add while stirring the 20mL vitriol oil, in cooling rear immigration 1000mL volumetric flask, be diluted with water to graticule, shake up, before use, demarcate with potassium bichromate standardized solution;
Being formulated as of sulfuric acid-silver sulfate solution: add 5g Sulfuric acid disilver salt in the 500mL vitriol oil, place 1-2d, frequently shake and make its dissolving;
Mercury bisulfate is: crystallization or powder.
Further, the concrete grammar that potassium bichromate standardized solution is demarcated is:
Accurately draw 10.00mL potassium bichromate standardized solution in 250mL Erlenmeyer flask, be diluted with water to 110mL, slowly add the 30mL vitriol oil, mix, after cooling, adding 3 phenanthroline ion indicating liquids is 0.15mL, uses l ferrous ammonium sulfate solution titration, the color of solution is terminal by yellow through blue-greenish colour to sorrel
C＝0.2500×10.00/V
In formula: the concentration of C---ferrous ammonium sulphate standardized solution;
The consumption of V---ferrous ammonium sulphate standardized solution.
The treatment process of glyphosate waste water provided by the invention, the rate of recovery that obtains glyphosate by replacement(metathesis)reaction reaches 97.8%, advantages of good adsorption effect, treatment process provided by the invention is through having carried out a large amount of experiments to conditions such as the temperature of proportioning, various operations between each composition, times, thereby determine processing the reasonable component proportioning of glyphosate waste water, operational condition and the most reasonable approach, reached the good effect of processing glyphosate waste water, for carrying out energy-saving and emission-reduction and realizing Sustainable Socioeconomic Development and make very large contribution.In addition, the inventive method is simple, easy to operate, has effectively processed glyphosate waste water, has protected environment.
Accompanying drawing explanation
Fig. 1 is the schema of the treatment process of the glyphosate waste water that provides of the embodiment of the present invention;
Fig. 2 is the typical curve schematic diagram of the glyphosate that provides of the embodiment of the present invention;
Fig. 3 is the schematic diagram of the mol ratio of the glyphosate that provides of the embodiment of the present invention and aluminum chloride;
Fig. 4 is the schematic diagram of the mol ratio that provides of the embodiment of the present invention to glyphosate clearance;
Fig. 5 is the affect schematic diagram of the temperature that provides of the embodiment of the present invention on glyphosate clearance;
Fig. 6 is the affect schematic diagram of the churning time that provides of the embodiment of the present invention on glyphosate clearance;
Fig. 7 is the affect schematic diagram of the mol ratio that provides of the embodiment of the present invention on CODcr;
Fig. 8 is the affect schematic diagram of the temperature that provides of the embodiment of the present invention on CODcr;
Fig. 9 is the affect schematic diagram of the churning time that provides of the embodiment of the present invention on CODcr;
Figure 10 is the schematic diagram of the impact of the sodium-chlor that provides of the embodiment of the present invention.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Fig. 1 shows the process flow of glyphosate waste water provided by the invention.For convenience of explanation, only show part related to the present invention.
The treatment process of the glyphosate waste water of the embodiment of the present invention, the treatment process of this glyphosate waste water comprises the following steps:
As a prioritization scheme of the embodiment of the present invention, in step 2, electric heating constant-temperature blowing drying box is set to 50 ℃.
As a prioritization scheme of the embodiment of the present invention, in step 3, the concrete grammar of glyphosate nitrosylation is:
With transfer pipet, accurately draw with the filtrate 10mL of filter filtration in 100mL volumetric flask, add successively 0.5mL sulphuric acid soln, 0.1mL potassium bromide solution, 0.5mL sodium nitrite solution, rapidly by stopper jam-pack, fully shake up, place 20min, with distilled water diluting to scale, shake up, open stopper, place 10min, nitrite acidizing temperature of reaction is greater than 15 ℃.
As a prioritization scheme of the embodiment of the present invention, being formulated as of sulphuric acid soln: the volume ratio of sulfuric acid and water is to be mixed with 50% sulphuric acid soln at 1: 1.
As a prioritization scheme of the embodiment of the present invention, being formulated as of sodium nitrite solution: take 0.28g Sodium Nitrite, be dissolved in 20mL distilled water.
As a prioritization scheme of the embodiment of the present invention, being formulated as of KBr solution: accurately take 25gKBr and be surely dissolved in 100mL volumetric flask.
As a prioritization scheme of the embodiment of the present invention, the concrete grammar of step 4 is:
The first step, gets the glyphosate waste water treatment solution of 5.00mL, is diluted to 100mL;
Second step, the water sample of getting 20.00mL dilution is placed in the backflow Erlenmeyer flask of 250mL ground, take the Mercury bisulfate of 0.4g, add 10.00mL potassium bichromate standardized solution and several little granulated glass spherees or zeolite, the spherical condensation tube that connects ground, from the prolong 30mL sulfuric acid-silver sulfate solution that adds at leisure suitable for reading, shake gently Erlenmeyer flask solution is evenly mixed, reflux 2h;
The 3rd step, cooling after, with 90mL distilled water, by prolong is suitable for reading, slowly pour into, take off Erlenmeyer flask, overall solution volume is not less than 140mL;
The 4th step, after solution is again cooling, adds 3 phenanthroline ion indicating liquids, and with the titration of ferrous ammonium sulphate standardized solution, the color of solution is terminal by yellow through blue-greenish colour to sorrel, records the consumption of ferrous ammonium sulphate standardized solution;
The 5th step, when measuring water sample, gets 20.00mL distilled water, by same operation steps, does blank test, the consumption of ferrous ammonium sulphate standardized solution when blank measured in record;
Calculation formula:
CODcr(O
2，mg/L)＝[(V
0-V
1)×C×8×1000]/V
In formula: the concentration of C---ferrous ammonium sulphate standardized solution;
The consumption of ferrous ammonium sulphate standardized solution when V0---titration is blank;
The consumption of ferrous ammonium sulphate standardized solution during V1---Titration Water Sample;
The volume of V---water sample;
8---oxygen (1/2O) molar mass.
As a prioritization scheme of the embodiment of the present invention, being formulated as of potassium bichromate standardized solution: potassium bichromate is dried to 2h to mass conservation at 120 ℃, accurately take 3.0645g soluble in water, move into 250mL volumetric flask, be diluted to standard lines, shake up;
Being formulated as of phenanthroline ion indicating liquid: take the adjacent luxuriant and rich with fragrance sound of vomiting of 1.485g quinoline, 0.695g ferrous sulfate is soluble in water, is diluted to 100mL, be stored in brown bottle;
Being formulated as of ferrous ammonium sulphate standardized solution: take 39.5g ferrous ammonium sulphate soluble in water, slowly add while stirring the 20mL vitriol oil, in cooling rear immigration 1000mL volumetric flask, be diluted with water to graticule, shake up, before use, demarcate with potassium bichromate standardized solution;
Being formulated as of sulfuric acid-silver sulfate solution: add 5g Sulfuric acid disilver salt in the 500mL vitriol oil, place 1-2d, frequently shake and make its dissolving;
Mercury bisulfate is: crystallization or powder.
As a prioritization scheme of the embodiment of the present invention, the concrete grammar that potassium bichromate standardized solution is demarcated is:
Accurately draw 10.00mL potassium bichromate standardized solution in 250mL Erlenmeyer flask, be diluted with water to 110mL, slowly add the 30mL vitriol oil, mix, after cooling, adding 3 phenanthroline ion indicating liquids is 0.15mL, uses l ferrous ammonium sulfate solution titration, the color of solution is terminal by yellow through blue-greenish colour to sorrel
C＝0.2500×10.00/V
In formula: the concentration of C---ferrous ammonium sulphate standardized solution;
The consumption of V---ferrous ammonium sulphate standardized solution.
Below in conjunction with drawings and the specific embodiments, application principle of the present invention is further described.
As shown in Figure 1, the treatment process of the glyphosate waste water of the embodiment of the present invention comprises the following steps:
S101: the glyphosate of title 1.0000g95% adds the distilled water of 100mL, is dissolved in beaker.The aluminum chloride accurately taking again, the mol ratio of glyphosate and aluminum chloride is 1: 4, adds in beaker and dissolves, with the pH of sodium hydrate regulator solution, be then neutral, afterwards, at 30 ℃, churning time is 9 hours;
S102: filter, dry, use vacuum pump using circulatory water that treatment solution is carried out to suction filtration, then filter cake is put into the electric heating constant-temperature blowing drying box of 50 ℃ dry;
S103: the filtrate of handling is measured to volume, and carry out nitrosylation, detect with ultraviolet spectrophotometer, and the filter cake being dried is carried out to infrared spectra detection;
S104: the content of test organic pollutant;
By following experiment, the present invention is described further:
Agilengt8453 ultraviolet spectrophotometer, Fourier transformation infrared spectrometer, electronic balance (Shimaozu Corporation Japan), electric heating air blast thermostatic drying chamber 01-1 (Longkou City Huang Cheng lean electric furnace factory), air drying device for glass articles (Hua Lu electric heating Instrument Ltd.), vacuum pump using circulatory water (Henan Yu Hua Instrument Ltd.), electronic stirrer (manufacture of Jintan, Jiangsu Province Medical Instruments factory), filtration unit, magnetic force heating stirrer 78-1 (, Community of Jin Tan County city sunlight instrument plant), round-bottomed flask, spherical condensation tube, microthrmometer, syringe, volumetric flask, glass stick, graduated cylinder, beaker, thermometer, acid buret, drip measuring bottle, transfer pipet, rubber pipette bulb, iron stand,
1, experimental technique
Single factor experiment
Table 1 single factor design
1. accurately claim the glyphosate of 1.0000g95% to add the distilled water of 100mL, be dissolved in beaker, then the aluminum chloride that accurately takes certain mass adds in beaker and dissolves, then with the pH of sodium hydrate regulator solution, be neutral, afterwards, at 30 ℃, churning time is under 12 hours, with certain rotating speed, stirs;
2. filter, dry, use vacuum pump using circulatory water that treatment solution is carried out to suction filtration, then filter cake is put into the electric heating constant-temperature blowing drying box of 50 ℃ dry;
3. detect, the filtrate of handling is measured to volume, and carry out nitrosylation, with ultraviolet spectrophotometer, detect, and the filter cake being dried is carried out to infrared spectra detection;
4. survey COD content;
Orthogonal test, experimental design is as follows:
Table 2 orthogonal experimental design
Step is copied an experiment,
Simultaneous test, experimental design is as follows:
The design of table 3 simultaneous test
Under the condition that is 1: 4 in the mol ratio of glyphosate and aluminum chloride, carry out, experimental procedure is an experiment as above,
The method of 2 glyphosate nitrosylations
(1) preparation of solution
1. the preparation of sulphuric acid soln: the volume ratio of sulfuric acid and water is to be mixed with 50% sulphuric acid soln at 1: 1,
2. the preparation of sodium nitrite solution: take 0.28g Sodium Nitrite (being accurate to 0.001g), be dissolved in 20mL distilled water, this solution is now with the current,
3. KBr solution: accurately take 25gKBr and be surely dissolved in 100mL volumetric flask, (this series solution time limit of service is within 20 days);
(2) operation steps
With transfer pipet, accurately draw with the filtrate 10mL of filter filtration in 100mL volumetric flask, add successively 0.5mL sulphuric acid soln, 0.1mL potassium bromide solution, 0.5mL sodium nitrite solution (matching while using), rapidly plug is given to jam-pack, fully shake up, place 20min, with distilled water diluting to scale, shake up, open stopper, place 10min, nitrite acidizing temperature of reaction can not be lower than 15 ℃;
3, the mensuration of COD
(1) preparation of solution
1. potassium bichromate standardized solution (1/6K
2cr
2o
7): in advance potassium bichromate is dried to 2h to mass conservation at 120 ℃, accurately take 3.0645g soluble in water, move into 250mL volumetric flask, be diluted to standard lines, shake up;
2. phenanthroline ion indicating liquid: take the adjacent luxuriant and rich with fragrance sound of vomiting quinoline (C of 1.485g
12h
8n
2h
2o), 0.695g ferrous sulfate (FeSO
47H
2o) soluble in water, be diluted to 100mL, be stored in brown bottle;
3. ferrous ammonium sulphate standardized solution (Fe (NH
4)
2(SO
4)
26H
2o): take 39.5g ferrous ammonium sulphate soluble in water, slowly add while stirring the 20mL vitriol oil, in cooling rear immigration 1000mL volumetric flask, be diluted with water to graticule, shake up, before use, with potassium bichromate standardized solution, demarcate;
Scaling method: accurately draw 10.00mL potassium bichromate standardized solution in 250mL Erlenmeyer flask, be diluted with water to 110mL left and right, slowly add the 30mL vitriol oil, mix, after cooling, add 3 phenanthroline ion indicating liquids (about 0.15mL), use l ferrous ammonium sulfate solution titration, the color of solution is terminal by yellow through blue-greenish colour to sorrel
C＝0.2500×10.00/V
In formula: the concentration (mol/L) of C---ferrous ammonium sulphate standardized solution;
The consumption (mL) of V---ferrous ammonium sulphate standardized solution,
4. sulfuric acid-silver sulfate solution: in the 500mL vitriol oil, add 5g Sulfuric acid disilver salt, place 1-2d, frequently shake it is dissolved,
5. Mercury bisulfate: crystallization or powder,
(2) determination step
1. the glyphosate waste water treatment solution of getting 5.00mL, is diluted to 100mL;
2. the water sample of getting 20.00mL dilution is placed in the backflow Erlenmeyer flask of 250mL ground, take the Mercury bisulfate of 0.4g, accurately add 10.00mL potassium bichromate standardized solution and several little granulated glass spherees or zeolite, the spherical condensation tube that connects ground, from the prolong 30mL sulfuric acid-silver sulfate solution that adds at leisure suitable for reading, shake gently Erlenmeyer flask solution is evenly mixed, reflux 2h (timing while certainly coming to life);
3. after cooling, with 90mL distilled water, by prolong is suitable for reading, slowly pour into, take off Erlenmeyer flask, overall solution volume must not be less than 140mL;
4. solution again cooling after, add 3 phenanthroline ion indicating liquids, with the titration of ferrous ammonium sulphate standardized solution, the color of solution is terminal by yellow through blue-greenish colour to sorrel, records the consumption of ferrous ammonium sulphate standardized solution;
When 5. measuring water sample, get 20.00mL distilled water, by same operation steps, do blank test, the consumption of ferrous ammonium sulphate standardized solution when blank measured in record;
Calculate:
CODcr(O
2，mg/L)＝[(V
0-V
1)×C×8×1000]/V
In formula: the concentration (mol/L) of C---ferrous ammonium sulphate standardized solution;
The consumption (mL) of ferrous ammonium sulphate standardized solution when V0---titration is blank;
The consumption of ferrous ammonium sulphate standardized solution (mL) during V1---Titration Water Sample;
The volume of V---water sample (mL);
8---oxygen (1/2O) molar mass (g/mol),
4, glyphosate Specification Curve of Increasing, as shown in Figure 2,
(1) preparation of standard solution: the solution of preparation 1g/L, dilutes respectively 1.5 times, 2 times, 3 times, 4 times, 8 times;
(2) nitrite acidizing: accurately draw glyphosate standard solution and six kinds of diluent 10.00mL in 6 100mL volumetric flasks with transfer pipet respectively, separately get a 100mL volumetric flask and do reagent blank simultaneously, in above-mentioned solution, add successively 0.5mL sulphuric acid soln, 0.1mL potassium bromide solution, 0.5mL sodium nitrite solution (matching while using), rapidly by stopper jam-pack, fully shake up, place 20min, with distilled water diluting to scale, shake up, open stopper, place 15min, nitrite acidizing temperature of reaction can not be lower than 15 ℃;
(3) with ultraviolet spectrophotometer, measure the absorbancy of a series of concentration glyphosate solution, with absorbancy, concentration is mapped and obtained the typical curve of glyphosate, fit equation is: y=-0.02031+0.29033x, and coefficient R 2=0.99861 analyzes the glyphosate in sample solution; ;
5, the conclusion of experiment:
Single factor experiment
As shown in Figure 3, along with reducing of the mol ratio of glyphosate and aluminum chloride, in treatment solution, the removal of glyphosate takes the lead in increasing and reduces, and the mol ratio of glyphosate and aluminum chloride 1: 4 o'clock, the treatment effect of waste water was best, this is because of the increase along with aluminum chloride input amount, the co-precipitation amount generating increases, and the clearance of glyphosate also can improve, but when the input amount of aluminum chloride is increased to 5 times, due to the impact of salt effect, common-ion effcet, the clearance of glyphosate reduces;
The orthogonal experiments of the removal effect of glyphosate and analysis
In table 4, by P, be worth, the mol ratio of glyphosate and aluminum chloride, temperature and churning time on the clearance of glyphosate without too large impact, by FC > FB > FA, drawn, the primary and secondary order of each factor on the clearance impact of glyphosate: the mol ratio of churning time > temperature > glyphosate and aluminum chloride, for the mol ratio of glyphosate and aluminum chloride, K2 > K1 > K3, so the mol ratio of glyphosate and aluminum chloride is to be at 1: 4 optimum level, in like manner the optimum level of temperature is 30 ℃, the optimum level of churning time is 9 hours, thereby, for the clearance of glyphosate, preferred embodiment is that the mol ratio of glyphosate and aluminum chloride is 1: 4, 30 ℃ of temperature, churning time is 9 hours,
Table 4 orthogonal test analysis and result
Variance is divided watchman's clapper table
Note: F0.05 (2,2)=19; F0.1 (2,2)=9,
The impact of mol ratio on the clearance of glyphosate
As shown in Figure 4, along with reducing of the mol ratio of glyphosate and aluminum chloride, in treatment solution, the removal of glyphosate takes the lead in increasing and reduces, and the mol ratio of glyphosate and aluminum chloride 1: 4 o'clock, the treatment effect of waste water was best, this is because of the increase along with aluminum chloride input amount, the co-precipitation amount generating increases, and the clearance of glyphosate also can improve, but when the input amount of aluminum chloride is increased to 5 times, due to the impact of salt effect, common-ion effcet, the clearance of glyphosate reduces;
The impact of temperature on the clearance of glyphosate
As shown in Figure 5, along with the rising of temperature, in treatment solution, the removal of glyphosate takes the lead in increasing and reduces, when 30 ℃ of temperature, glyphosate clearance is best, and reason is to raise with temperature, reactant activity increases, and the precipitation of generation increases, and the clearance of glyphosate increases, with temperature, by 30 ℃-40 ℃, this exothermic heat of reaction, makes molecular balance carry out to contrary direction, simultaneous temperature is too high, solubleness increases, and is unfavorable for the absorption of glyphosate, and glyphosate clearance is reduced;
The impact of churning time on glyphosate clearance
As shown in Figure 6, during beginning, with the prolongation of churning time, the clearance of glyphosate increases, and reason is growth in time, reacts more abundant, deposit seeds constantly reduces, and its surface-area constantly increases, and glyphosate adsorptive capacity is on the increase, reaction reaches balance, but churning time is during by 9-12h, and reaction has reached balance, the prolongation of churning time on the removal effect of glyphosate without too large impact, likely occur that on the contrary reaction is to carrying out against direction, removal effect reduces;
The orthogonal experiments of CODcr clearance and analysis
Table 5 orthogonal test analysis and result
Analysis of variance table
Note: F0.05 (2,2)=19; F0.01 (2,2)=9,
In table 5, by P, be worth, the mol ratio of glyphosate and aluminum chloride, temperature and churning time on the clearance of COD without too large impact, by FA > FB > FC, drawn, the primary and secondary order of each factor on the clearance impact of COD: the mol ratio > temperature > churning time of glyphosate and aluminum chloride, for the mol ratio of glyphosate and aluminum chloride, K1 > K2 > K3, so the mol ratio of glyphosate and aluminum chloride is to be at 1: 3 optimum level, in like manner the optimum level of temperature is 40 ℃, the optimum level of churning time is 12 hours, thereby, for the clearance of COD, preferred embodiment is that the mol ratio of glyphosate and aluminum chloride is 1: 3, 40 ℃ of temperature, churning time is 12 hours,
The impact of the mol ratio of glyphosate and aluminum chloride on the clearance of CODcr
As shown in Figure 7, along with the increase of the add-on of aluminum chloride, the clearance of CODcr constantly reduces, reason may be the increase along with the add-on of aluminum chloride, and the amount of sodium hydroxide also increases thereupon, has a large amount of Na+ in solution, Cl+, with the increase of inorganic salt in solution, CODcr also increases thereupon;
The impact of temperature on the clearance of CODcr
As shown in Figure 8, along with the rising of temperature, the clearance of CODcr also increases slightly, but totally it seems, impact is also little;
The impact of churning time on the clearance of CODcr
As shown in Figure 9, along with the prolongation of churning time, the clearance of CODcr also increases slightly, reason may be that hetero-ion and the impurity absorption in solution constantly increases in the amount of precipitation, but, may error ratio in the measurement of COD larger, and affect in general not remarkable;
The impact of sodium-chlor
Mol ratio at glyphosate and aluminum chloride is 1: 4, and temperature is 30 ℃, and churning time is 9 hours,
The impact of table 6 sodium-chlor
As shown in Figure 10, along with increasing of sodium-chlor add-on, the clearance of glyphosate reduces a little, but the amplitude reducing is little; The clearance of COD enlarges markedly;
6, sum up
(1) by single factor experiment, shown that the impact of mol ratio is V-shaped, glyphosate removal effect first improves along with the reducing of mol ratio of glyphosate and aluminum chloride; Until mol ratio is 1: 4 o'clock, treatment effect is best; Afterwards, along with reducing of mol ratio, reduce;
(2) known by orthogonal test, in the mol ratio of glyphosate and aluminum chloride, be 1: 4, temperature is 30 ℃, when churning time is 9 hours, the clearance of glyphosate is best, and these three factors are smaller on the impact of the clearance of glyphosate;
(3) known by orthogonal test, in the mol ratio of glyphosate and aluminum chloride, be 1: 3, temperature is 40 ℃, when churning time is 12 hours, the clearance of CODcr is best, and the impact of the mol ratio of glyphosate and aluminum chloride is the most remarkable;
(4) known by simultaneous test, the add-on of sodium-chlor is not remarkable on the clearance impact of glyphosate, but the clearance of COD increases gradually with the add-on of sodium-chlor.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a treatment process for glyphosate waste water, is characterized in that, the treatment process of this glyphosate waste water comprises the following steps:
Step 1, the glyphosate of title 1.0000g95% adds the distilled water of 100mL, is dissolved in beaker, the aluminum chloride taking again, the mol ratio of glyphosate and aluminum chloride is 1: 4, adds in beaker and dissolves, then with the pH of sodium hydrate regulator solution, being neutral, is 9 hours 30 ℃ of churning time;
Step 2, filters, dries, and uses vacuum pump using circulatory water that treatment solution is carried out to suction filtration, then filter cake is put into electric heating constant-temperature blowing drying box dries;
Step 3, measures volume by the filtrate of handling, and carries out nitrosylation, detects, and the filter cake being dried is carried out to infrared spectra detection with ultraviolet spectrophotometer;
Step 4, the content of test organic pollutant.
2. the treatment process of glyphosate waste water as claimed in claim 1, is characterized in that, in step 2, electric heating constant-temperature blowing drying box is set to 50 ℃.
3. the treatment process of glyphosate waste water as claimed in claim 1, is characterized in that, in step 3, the concrete grammar of glyphosate nitrosylation is:
With transfer pipet, accurately draw with the filtrate 10mL of filter filtration in 100mL volumetric flask, add successively 0.5mL sulphuric acid soln, 0.1mL potassium bromide solution, 0.5mL sodium nitrite solution, rapidly by stopper jam-pack, fully shake up, place 20min, with distilled water diluting to scale, shake up, open stopper, place 10min, nitrite acidizing temperature of reaction is greater than 15 ℃.
4. the treatment process of glyphosate waste water as claimed in claim 3, is characterized in that, being formulated as of sulphuric acid soln: the volume ratio of sulfuric acid and water is to be mixed with 50% sulphuric acid soln at 1: 1.
5. the treatment process of glyphosate waste water as claimed in claim 3, is characterized in that, being formulated as of sodium nitrite solution: take 0.28g Sodium Nitrite, be dissolved in 20mL distilled water.
6. the treatment process of glyphosate waste water as claimed in claim 3, is characterized in that, being formulated as of KBr solution: take 25gKBr and be surely dissolved in 100mL volumetric flask.
7. the treatment process of glyphosate waste water as claimed in claim 1, is characterized in that, the concrete grammar of step 4 is:
The first step, gets the glyphosate waste water treatment solution of 5.00mL, is diluted to 100mL;
Second step, the water sample of getting 20.00mL dilution is placed in the backflow Erlenmeyer flask of 250mL ground, take the Mercury bisulfate of 0.4g, add 10.00mL potassium bichromate standardized solution and several little granulated glass spherees or zeolite, the spherical condensation tube that connects ground, from the prolong 30mL sulfuric acid-silver sulfate solution that adds at leisure suitable for reading, shake gently Erlenmeyer flask solution is evenly mixed, reflux 2h;
The 3rd step, cooling after, with 90mL distilled water, by prolong is suitable for reading, slowly pour into, take off Erlenmeyer flask, overall solution volume is not less than 140mL;
The 4th step, after solution is again cooling, adds 3 phenanthroline ion indicating liquids, and with the titration of ferrous ammonium sulphate standardized solution, the color of solution is terminal by yellow through blue-greenish colour to sorrel, records the consumption of ferrous ammonium sulphate standardized solution;
The 5th step, when measuring water sample, gets 20.00mL distilled water, by same operation steps, does blank test, the consumption of ferrous ammonium sulphate standardized solution when blank measured in record;
Calculation formula:
CODcr(O
2，mg/L)＝[(V0-V1)×C×8×1000]/V
In formula: the concentration of C---ferrous ammonium sulphate standardized solution;
The consumption of ferrous ammonium sulphate standardized solution when V0---titration is blank;
The consumption of ferrous ammonium sulphate standardized solution during V1---Titration Water Sample;
The volume of V---water sample;
8---oxygen (1/2O) molar mass.
8. the treatment process of glyphosate waste water as claimed in claim 7, is characterized in that, being formulated as of potassium bichromate standardized solution: potassium bichromate is dried to 2h to mass conservation at 120 ℃, take 3.0645
gsoluble in water, move into 250mL volumetric flask, be diluted to standard lines, shake up;
Being formulated as of phenanthroline ion indicating liquid: take the adjacent luxuriant and rich with fragrance sound of vomiting of 1.485g quinoline, 0.695g ferrous sulfate is soluble in water, is diluted to 100mL, be stored in brown bottle;
Being formulated as of ferrous ammonium sulphate standardized solution: take 39.5g ferrous ammonium sulphate soluble in water, slowly add while stirring the 20mL vitriol oil, in cooling rear immigration 1000mL volumetric flask, be diluted with water to graticule, shake up, before use, demarcate with potassium bichromate standardized solution;
Being formulated as of sulfuric acid-silver sulfate solution: add 5g Sulfuric acid disilver salt in the 500mL vitriol oil, place 1-2d, frequently shake dissolving;
Mercury bisulfate is: crystallization or powder.
9. the treatment process of glyphosate waste water as claimed in claim 8, is characterized in that, the concrete grammar that potassium bichromate standardized solution is demarcated is:
Draw 10.00mL potassium bichromate standardized solution in 250mL Erlenmeyer flask, be diluted with water to 110mL, slowly add the 30mL vitriol oil, mix, after cooling, adding 3 phenanthroline ion indicating liquids is 0.15mL, uses l ferrous ammonium sulfate solution titration, the color of solution is terminal by yellow through blue-greenish colour to sorrel
C＝0.2500×10.00/V
In formula: the concentration of C---ferrous ammonium sulphate standardized solution;
The consumption of V---ferrous ammonium sulphate standardized solution.
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| CN105314762A (en) * | 2014-07-31 | 2016-02-10 | 江苏扬农化工股份有限公司 | Comprehensive treatment method for glyphosate wastewater |
| CN115178225A (en) * | 2022-06-21 | 2022-10-14 | 武汉工程大学 | Aluminum-titanium bimetal doped mesoporous silica, preparation method thereof and application thereof in adsorbing glyphosate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105314762A (en) * | 2014-07-31 | 2016-02-10 | 江苏扬农化工股份有限公司 | Comprehensive treatment method for glyphosate wastewater |
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| CN115178225A (en) * | 2022-06-21 | 2022-10-14 | 武汉工程大学 | Aluminum-titanium bimetal doped mesoporous silica, preparation method thereof and application thereof in adsorbing glyphosate |
| CN115178225B (en) * | 2022-06-21 | 2023-11-17 | 武汉工程大学 | Aluminum-titanium bimetal doped mesoporous silica, preparation method thereof and application thereof in adsorption of glyphosate |
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