CN103523887B - Treatment method for glyphosate wastewater - Google Patents
Treatment method for glyphosate wastewater Download PDFInfo
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- CN103523887B CN103523887B CN201310460343.1A CN201310460343A CN103523887B CN 103523887 B CN103523887 B CN 103523887B CN 201310460343 A CN201310460343 A CN 201310460343A CN 103523887 B CN103523887 B CN 103523887B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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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, particularly relate 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 at about 48000-52000mg/L, also contain the inorganic salt of about 15%, as sodium-chlor (NaCl), therefore, most of manufacturing enterprise of current China by add after this Waste water concentrating a certain amount of glyphosate dry powder and auxiliary agent make massfraction be 10% gyphosate solution sell, but like this, inorganic salt a large amount of in waste water and organism are brought in farmland, soil compaction and salinization will be caused further, and the pollution of water body, so lot of domestic and foreign scientific research personnel this has been a large amount of research work, main employing physico-chemical processes, 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 glyphosate is made to generate calcium precipitation with CaC12 solution as precipitation agent, obtain through tenderizer process the glyphosate aqueous solution that massfraction is 5% after precipitation, the rate of recovery of this technique glyphosate reaches 95%, CODcr clearance is greater than 95%, adequately achieve 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 after reclaiming catalyzer, add excessive calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, calcium salt or magnesium salts, filter after abundant reaction, obtain the filter cake of the magnesium salts of calcium salt containing glyphosate or glyphosate, filter cake mineral acid treatment is obtained 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 process of metathesis combined recovery glyphosate and the research of utilization approaches, the clearance of glyphosate reaches more than 95%, appropriate Na is added when reclaiming
2cO
3, the rate of recovery being obtained 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, current lot of domestic and foreign scientific research personnel is just studying glyphosate and heavy metal ion on various common adsorbents, the adsorption mechanism of inorganic phosphate radical ion etc. and Adsorption Model, such as: activated alumina has good adsorption-desorption treatment effect to glyphosate, after 10mL A1-1 alumina adsorption process glyphosate waste water, the clearance of glyphosate reaches more than 98%, COD clearance reaches 50%, the maximum adsorption capacity of activated carbon supported hydrous iron oxide absorption method to glyphosate reaches 120mg/g, 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 to wait with D301R macroporous weakly basic anion exchange resin as sorbent material, result CODcr clearance reaches 96%, and the CLT acid can effectively removed in waste water, Xiao Gu waits clearly and finds the Study on adsorption properties of glyphosate with 330 anionite-exchange resin, cooling is conducive to absorption, NaCl content increases, adsorption effect significantly reduces,
(3) chemical oxidization method
Chlorine oxidation process is with hydrochloric acid by glyphosate mother solution acidifying adjust pH, then adds sodium chlorate solution and react to obtain dioxide peroxide, Chlorine Dioxide Oxidation glyphosate and other organism afterwards, and obtaining glyphosate rate of decomposition is about 70%;
Hydrogen peroxide oxidation method uses hydrogen peroxide oxidation glyphosate mother solution, go forward side by side oxidation step glyphosate and other organism, and obtain small molecules or inorganics through oxidation organic macromolecule, now glyphosate rate of decomposition reaches about 40%,
Also has High Temperature High Pressure catalytic oxidation, the ultra-violet oxidation method etc. of special wavelength;
(4) biochemical process
The novel anaerobic baffled reactor (ABR) such as Cao Xiaoying processes glyphosate waste water, when raw wastewater CODcr mass concentration is within the scope of 6000-7000mg/L, the HRT arranging reactor is 15-18h, under mesophilic condition, after process, the clearance of CODcr reaches 95.6%, and pollutants removal rate is up to more than 95%;
(5) advanced oxidation processes
The Fendon reagent such as Liao Huan carrys 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 can removed in glyphosate waste water, alleviate the pressure of subsequent biochemical process, the Fendon photocatalysis degradation glyphosate waste water such as Gu Yan, 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, have employed Fenton-Mg (OH)
2method process glyphosate waste water, first with the organism of Fenton reagent oxidation difficult degradation, use adsorption of magnesium hydroxide settlement treatment again, can not only organics removal effectively, and COD clearance can up to more than 76%, Fu Guanglong etc., in the test of Fenton reagent process glyphosate waste water, draw and are 30min in pH=3, reaction times, under temperature of reaction is the condition of 60 DEG C, 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. are in the research of Oxidation Pretreatment of Wastewater from Glyphosate Production with Sodium Hypochlorite, and obtain in former alkaline waste water, clorox add-on is equivalent to the available chlorine of theoretical amount 40%, reacts 4h under room temperature, and the clearance of glyphosate can reach 98%;
(, 6) and combination treatment method
Zhang Huanzhen etc. process by the glyphosate waste water selectivity organism reactor-UASB-CAAS combination process after electrolysis pretreatment, first remove chlorion by electrolysis treatment, selectivity organism reactor (UASB) and up-flow anaerobic sludge blanket is adopted to remove most organic pollutant (COD) again, finally use Anoxic/Aerobic combined system (CAAS) to process, after process, COD clearance reaches 99%;
Tang Jie etc. adopt multi-dimensional electro-catalytic art breading glyphosate mother solution, and COD clearance all reaches about 85%, and total tp removal rate reaches 90%;
(7) membrane separation concentration method
Membrane separation technique is an emerging technology in recent years, by the selective penetrated property energy separating mixture of film, purification and the concentrated new separation technology drawing object product.
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 the treatment process providing a kind of glyphosate waste water, and be intended to solve existing glyphosate waste water treatment process and there is complicated operation, 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:
Step one, claims the glyphosate of 1.0000g95% to add the distilled water of 100mL, is dissolved in beaker, the aluminum chloride accurately taken again, the mol ratio of glyphosate and aluminum chloride is 1: 4, adds in beaker and dissolves, then being neutral with the pH of sodium hydrate regulator solution, is 9 hours 30 DEG C of churning time;
Step 2, filters, dries, and uses vacuum pump using circulatory water that treatment solution is carried out suction filtration, then filter cake is put into electric heating constant-temperature blowing drying box dries;
Step 3, measures volume by the filtrate processed, and carries out nitrosylation, detects, and filter cake complete for drying is carried out infrared spectra detection with ultraviolet spectrophotometer;
Step 4, the content of test organic pollutant.
Further, in step 2, electric heating constant-temperature blowing drying box is set to 50 DEG C.
Further, in step 3, the concrete grammar of glyphosate nitrosylation is:
With transfer pipet accurately the filtrate 10mL that filters of absorption filter in 100mL volumetric flask, add 0.5mL sulphuric acid soln, 0.1mL potassium bromide solution, 0.5mL sodium nitrite solution successively, 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 DEG C.
Further, being formulated as of sulphuric acid soln: the volume ratio of sulfuric acid and water is 1: 1 sulphuric acid soln being mixed with 50%.
Further, being formulated as of sodium nitrite solution: take 0.28g Sodium Nitrite, is 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 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, connect the spherical condensation tube of ground, add 30mL sulfuric acid-silver sulfate solution at leisure from prolong is suitable for reading, shake Erlenmeyer flask gently and dissolution homogeneity is mixed, reflux 2h;
3rd step, after cooling, slowly pour into by prolong is suitable for reading with 90mL distilled water, take off Erlenmeyer flask, overall solution volume is not less than 140mL;
4th step, after solution cools again, adds 3 phenanthroline ion indicating liquids, and with the titration of ferrous ammonium sulphate standardized solution, the color from yellow of solution is terminal through blue-greenish colour to sorrel, the consumption of record ferrous ammonium sulphate standardized solution;
5th step, while measuring water sample, gets 20.00mL distilled water, does blank test by same operation steps, the consumption of ferrous ammonium sulphate standardized solution when record measures blank;
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 2h to mass conservation at 120 DEG C, accurately takes 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 quinoline of 1.485g, 0.695g ferrous sulfate is soluble in water, be 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 adds the 20mL vitriol oil while stirring, moves in 1000mL volumetric flask, be diluted with water to graticule, shake up, before use, demarcate with potassium bichromate standardized solution after cooling;
Being formulated as of sulfuric acid-silver sulfate solution: add 5g Sulfuric acid disilver salt in the 500mL vitriol oil, places 1-2d, and shake frequently makes it dissolve;
Mercury bisulfate is: crystallization or powder.
Further, the concrete grammar that potassium bichromate standardized solution is demarcated is:
Accurate absorption 10.00mL potassium bichromate standardized solution is in 250mL Erlenmeyer flask, be diluted with water to 110mL, slowly add the 30mL vitriol oil, mixing, after cooling, adding 3 phenanthroline ion indicating liquids is 0.15mL, uses l ferrous ammonium sulfate solution titration, the color from yellow of solution is terminal 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 being obtained 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 the condition such as temperature, time of proportioning, various operation between each composition, thus determine process glyphosate waste water most reasonable component proportioning, operational condition and the most reasonable approach, reach the good effect of process glyphosate waste water, make very large contribution for carrying out energy-saving and emission-reduction and realizing Sustainable Socioeconomic Development.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 the embodiment of the present invention provides;
Fig. 2 is the typical curve schematic diagram of the glyphosate that the embodiment of the present invention provides;
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 that the mol ratio that provides of the embodiment of the present invention is to the schematic diagram of glyphosate clearance;
Fig. 5 is that the temperature that provides of the embodiment of the present invention affects schematic diagram to glyphosate clearance;
Fig. 6 is that the churning time that provides of the embodiment of the present invention affects schematic diagram to glyphosate clearance;
Fig. 7 is that the mol ratio that provides of the embodiment of the present invention affects schematic diagram to CODcr;
Fig. 8 is that the temperature that provides of the embodiment of the present invention affects schematic diagram to CODcr;
Fig. 9 is that the churning time that provides of the embodiment of the present invention affects schematic diagram to CODcr;
Figure 10 is the schematic diagram of the impact of the sodium-chlor that the embodiment of the present invention provides.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, 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, be 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, illustrate only 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:
Step one, claims the glyphosate of 1.0000g95% to add the distilled water of 100mL, is dissolved in beaker, the aluminum chloride accurately taken again, the mol ratio of glyphosate and aluminum chloride is 1: 4, adds in beaker and dissolves, then being neutral with the pH of sodium hydrate regulator solution, is 9 hours 30 DEG C of churning time;
Step 2, filters, dries, and uses vacuum pump using circulatory water that treatment solution is carried out suction filtration, then filter cake is put into electric heating constant-temperature blowing drying box dries;
Step 3, measures volume by the filtrate processed, and carries out nitrosylation, detects, and filter cake complete for drying is carried out infrared spectra detection with ultraviolet spectrophotometer;
Step 4, the content of test organic pollutant.
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 DEG C.
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 the filtrate 10mL that filters of absorption filter in 100mL volumetric flask, add 0.5mL sulphuric acid soln, 0.1mL potassium bromide solution, 0.5mL sodium nitrite solution successively, 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 DEG C.
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 1: 1 sulphuric acid soln being mixed with 50%.
As a prioritization scheme of the embodiment of the present invention, being formulated as of sodium nitrite solution: take 0.28g Sodium Nitrite, is 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 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, connect the spherical condensation tube of ground, add 30mL sulfuric acid-silver sulfate solution at leisure from prolong is suitable for reading, shake Erlenmeyer flask gently and dissolution homogeneity is mixed, reflux 2h;
3rd step, after cooling, slowly pour into by prolong is suitable for reading with 90mL distilled water, take off Erlenmeyer flask, overall solution volume is not less than 140mL;
4th step, after solution cools again, adds 3 phenanthroline ion indicating liquids, and with the titration of ferrous ammonium sulphate standardized solution, the color from yellow of solution is terminal through blue-greenish colour to sorrel, the consumption of record ferrous ammonium sulphate standardized solution;
5th step, while measuring water sample, gets 20.00mL distilled water, does blank test by same operation steps, the consumption of ferrous ammonium sulphate standardized solution when record measures blank;
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 2h to mass conservation at 120 DEG C, accurately takes 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 quinoline of 1.485g, 0.695g ferrous sulfate is soluble in water, be 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 adds the 20mL vitriol oil while stirring, moves in 1000mL volumetric flask, be diluted with water to graticule, shake up, before use, demarcate with potassium bichromate standardized solution after cooling;
Being formulated as of sulfuric acid-silver sulfate solution: add 5g Sulfuric acid disilver salt in the 500mL vitriol oil, places 1-2d, and shake frequently makes it dissolve;
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:
Accurate absorption 10.00mL potassium bichromate standardized solution is in 250mL Erlenmeyer flask, be diluted with water to 110mL, slowly add the 30mL vitriol oil, mixing, after cooling, adding 3 phenanthroline ion indicating liquids is 0.15mL, uses l ferrous ammonium sulfate solution titration, the color from yellow of solution is terminal 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: claim the glyphosate of 1.0000g95% to add the distilled water of 100mL, be dissolved in beaker.The aluminum chloride accurately taken again, the mol ratio of glyphosate and aluminum chloride is 1: 4, adds in beaker and dissolves, and be then neutral with the pH of sodium hydrate regulator solution, afterwards, at 30 DEG C, churning time is 9 hours;
S102: filter, dry, use vacuum pump using circulatory water that treatment solution is carried out suction filtration, then electric heating constant-temperature blowing drying box filter cake being put into 50 DEG C is dried;
S103: the filtrate processed is measured volume, and carry out nitrosylation, detect with ultraviolet spectrophotometer, and filter cake complete for drying is carried out 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 (ShimaozuCorporation 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 (, sunlight instrument plant of Community of Jin Tan County city), 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 accurately taking certain mass adds in beaker and dissolves, then be neutral with the pH of sodium hydrate regulator solution, afterwards, at 30 DEG C, churning time is 12 at present little, stirs with certain rotating speed;
2. filter, dry, use vacuum pump using circulatory water that treatment solution is carried out suction filtration, then electric heating constant-temperature blowing drying box filter cake being put into 50 DEG C is dried;
3. detect, the filtrate processed is measured volume, and carry out nitrosylation, detect with ultraviolet spectrophotometer, and filter cake complete for drying is carried out infrared spectra detection;
4. COD content is surveyed;
Orthogonal test, experimental design is as follows:
Table 2 orthogonal experimental design
Step copies an experiment,
Simultaneous test, experimental design is as follows:
Table 3 simultaneous test designs
Carry out under the mol ratio of glyphosate and aluminum chloride is the condition of 1: 4, 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 1: 1 sulphuric acid soln being mixed with 50%,
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 serial solution time limit of service is within 20 days);
(2) operation steps
With transfer pipet accurately the filtrate 10mL that filters of absorption filter in 100mL volumetric flask, add 0.5mL sulphuric acid soln, 0.1mL potassium bromide solution, 0.5mL sodium nitrite solution (matching while using) successively, rapidly plug is given 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 lower than 15 DEG C;
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 2h to mass conservation at 120 DEG C, 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 the 20mL vitriol oil while stirring, move in 1000mL volumetric flask after cooling, be diluted with water to graticule, shake up, before use, demarcate with potassium bichromate standardized solution;
Scaling method: accurately draw 10.00mL potassium bichromate standardized solution in 250mL Erlenmeyer flask, be diluted with water to about 110mL, slowly add the 30mL vitriol oil, mixing, after cooling, add 3 phenanthroline ion indicating liquids (about 0.15mL), use l ferrous ammonium sulfate solution titration, the color from yellow of solution is terminal 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: add 5g Sulfuric acid disilver salt in the 500mL vitriol oil, places 1-2d, and shake frequently makes it dissolve,
5. Mercury bisulfate: crystallization or powder,
(2) determination step
1. get the glyphosate waste water treatment solution of 5.00mL, be diluted to 100mL;
2. the water sample 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, connect the spherical condensation tube of ground, 30mL sulfuric acid-silver sulfate solution is added at leisure from prolong is suitable for reading, shaking Erlenmeyer flask gently makes dissolution homogeneity mix, reflux 2h (when certainly coming to life timing);
3., after cooling, slowly pour into by prolong is suitable for reading with 90mL distilled water, take off Erlenmeyer flask, overall solution volume must not be less than 140mL;
4. after solution cools again, add 3 phenanthroline ion indicating liquids, with the titration of ferrous ammonium sulphate standardized solution, the color from yellow of solution is terminal through blue-greenish colour to sorrel, the consumption of record ferrous ammonium sulphate standardized solution;
5. while measuring water sample, get 20.00mL distilled water, do blank test by same operation steps, the consumption of ferrous ammonium sulphate standardized solution when record measures blank;
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 (mL) of ferrous ammonium sulphate standardized solution during V1---Titration Water Sample;
The volume (mL) of V---water sample;
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 1.5 times, 2 times, 3 times, 4 times, 8 times respectively;
(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 getting a 100mL volumetric flask does reagent blank simultaneously, 0.5mL sulphuric acid soln, 0.1mL potassium bromide solution, 0.5mL sodium nitrite solution (matching while using) is added successively in above-mentioned solution, 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 lower than 15 DEG C;
(3) absorbancy of a series of strength glyphosate solution is measured with ultraviolet spectrophotometer, the typical curve of glyphosate is obtained with Absorbance versus concentration mapping, 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 the reduction of the mol ratio of glyphosate and aluminum chloride, the removal for the treatment of solution glyphosate takes the lead in increasing and reduces, and mol ratio 1: 4 of glyphosate and aluminum chloride time, the treatment effect of waste water is best, this is because along with the increase of aluminum chloride input amount, the co-precipitation amount generated 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, be worth by P, the mol ratio of glyphosate and aluminum chloride, temperature and churning time on the clearance of glyphosate without too large impact, drawn by FC > FB > FA, the primary and secondary order that each factor affects the clearance 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 1: 4 is optimum level, in like manner the optimum level of temperature is 30 DEG C, the optimum level of churning time is 9 hours, thus, for the clearance of glyphosate, preferred embodiment is the mol ratio of glyphosate and aluminum chloride is 1: 4, temperature 30 DEG C, churning time is 9 hours,
Table 4 orthogonal test analysis and result
Variance divides watchman's clapper table
Note: F0.05 (2,2)=19; F0.1 (2,2)=9,
Mol ratio is on the impact of the clearance of glyphosate
As shown in Figure 4, along with the reduction of the mol ratio of glyphosate and aluminum chloride, the removal for the treatment of solution glyphosate takes the lead in increasing and reduces, and mol ratio 1: 4 of glyphosate and aluminum chloride time, the treatment effect of waste water is best, this is because along with the increase of aluminum chloride input amount, the co-precipitation amount generated 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;
Temperature is on the impact of the clearance of glyphosate
As shown in Figure 5, along with the rising of temperature, the removal for the treatment of solution glyphosate takes the lead in increasing and reduces, when temperature 30 DEG C, 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 DEG C-40 DEG C, this exothermic heat of reaction, makes molecular balance carry out to reverse direction, simultaneous temperature is too high, solubleness increases, and is unfavorable for the absorption of glyphosate, glyphosate clearance is reduced;
Churning time is on the impact of 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 when churning time is by 9-12h, reaction reaches balance, the prolongation of churning time on the removal effect of glyphosate without too large impact, likely occur that reaction is carried out to reverse direction on the contrary, 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, be worth by P, the mol ratio of glyphosate and aluminum chloride, temperature and churning time on the clearance of COD without too large impact, drawn by FA > FB > FC, the primary and secondary order that each factor affects the clearance 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 1: 3 is optimum level, in like manner the optimum level of temperature is 40 DEG C, the optimum level of churning time is 12 hours, thus, for the clearance of COD, preferred embodiment is the mol ratio of glyphosate and aluminum chloride is 1: 3, temperature 40 DEG C, churning time is 12 hours,
The mol ratio of glyphosate and aluminum chloride is on the impact of 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 of the add-on along with aluminum chloride, and the amount of sodium hydroxide also increases thereupon, there is a large amount of Na+ in solution, Cl+, with the increase of inorganic salt in solution, CODcr also increases thereupon;
Temperature is on the impact of 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;
Churning time is on the impact of 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 in solution and impurity absorption constantly increase in the amount of precipitation, but, in the measurement of COD may application condition large, and affect not remarkable in general;
The impact of sodium-chlor
Be 1: 4 in the mol ratio of glyphosate and aluminum chloride, temperature is 30 DEG C, 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 reduced 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, namely glyphosate removal effect first improves along with the reduction of the mol ratio of glyphosate and aluminum chloride; Until when mol ratio is 1: 4, treatment effect is best; Afterwards, reduce along with the reduction of mol ratio;
(2) known by orthogonal test, be 1: 4 in the mol ratio of glyphosate and aluminum chloride, temperature is 30 DEG C, and churning time is 9 constantly little, and the clearance of glyphosate is best, and these three factor impacts on the clearance of glyphosate are smaller;
(3) known by orthogonal test, be 1: 3 in the mol ratio of glyphosate and aluminum chloride, temperature is 40 DEG C, and churning time is 12 constantly little, and 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 clearance impact on glyphosate of the add-on of sodium-chlor is remarkable, 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 amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (1)
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 one, claims the glyphosate of 1.0000g 95% to add the distilled water of 100mL, is dissolved in beaker, take aluminum chloride again, the mol ratio of glyphosate and aluminum chloride is 1: 4, adds in beaker and dissolves, then being neutral with the pH of sodium hydrate regulator solution, is 9 hours 30 DEG C of churning time;
Step 2, filters, dries, and uses vacuum pump using circulatory water that treatment solution is carried out suction filtration, then filter cake is put into electric heating constant-temperature blowing drying box dries;
Step 3, measures volume by the filtrate processed, and carries out nitrosylation, detects, and filter cake complete for drying is carried out infrared spectra detection with ultraviolet spectrophotometer;
Step 4, the content of test organic pollutant;
In step 2, electric heating constant-temperature blowing drying box is set to 50 DEG C;
In step 3, the concrete grammar of glyphosate nitrosylation is:
With transfer pipet accurately the filtrate 10mL that filters of absorption filter in 100mL volumetric flask, add 0.5mL sulphuric acid soln, 0.1mL potassium bromide solution, 0.5mL sodium nitrite solution successively, 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 DEG C;
Being formulated as of sulphuric acid soln: the volume ratio of sulfuric acid and water is 1: 1 sulphuric acid soln being mixed with 50%;
Being formulated as of sodium nitrite solution: take 0.28g Sodium Nitrite, is dissolved in 20mL distilled water;
Being formulated as of KBr solution: take 25gKBr and be surely dissolved in 100mL volumetric flask.
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