CN104193061A - Treatment method for paraquat pesticide wastewater - Google Patents

Treatment method for paraquat pesticide wastewater Download PDF

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CN104193061A
CN104193061A CN201410441815.3A CN201410441815A CN104193061A CN 104193061 A CN104193061 A CN 104193061A CN 201410441815 A CN201410441815 A CN 201410441815A CN 104193061 A CN104193061 A CN 104193061A
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waste water
paraquat
hydrogen peroxide
treatment
salt
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CN104193061B (en
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张仲平
张毅
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SHAOXING QICAI CHEMICAL CO Ltd
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SHAOXING QICAI CHEMICAL CO Ltd
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Abstract

The invention discloses a treatment method for paraquat pesticide wastewater, and belongs to the technical field of treatment of the three wastes. The treatment method comprises the following steps: carrying out ozone oxidization, concentration and crystallization, and salt-leaching, introducing ozone for 1-2 hours after adding an adsorbent to completely oxidize cyanides; adding hydrogen peroxide to promote ozone oxidization speed, adding less hydrogen peroxide and then keeping the color of the mixture stable after the oxidization is ended, filtering to remove waste residues, and directly concentrating the obtained wastewater, rinsing the obtained salt with less washing water to reach industrial salt standards. The treatment method is applied to treating the paraquat pesticide wastewater, is relatively low in treatment cost, low in equipment requirement, low in operation cost, great in value of recycled salts and suitable for wastewater treatment of small and medium-sized enterprises.

Description

A kind for the treatment of process of Paraquat agricultural chemicals waste water
Technical field
The present invention relates to a kind for the treatment of process of Paraquat agricultural chemicals waste water, belong to disposal of three wastes technical field.
Background technology
Along with agriculture develop rapidly, kind and the consumption of agricultural chemicals also increase rapidly, and present stage, China's most of agricultural chemicals used all belongs to organic pesticide, and many have features such as large, the difficult decomposition of toxicity, and agricultural chemicals waste water becomes a great problem of water treatment field.Conventional method has at present: biochemical treatment, burning method, super oxidation etc.: biochemical treatment generally needs long-term acclimated microorganism, and effect is unstable, many agricultural chemicals can not thoroughly decompose, and part microorganism also can be transferred to the product that decomposition is more difficult, toxicity is stronger; The required condition of burning method is harsh, high cost, also easily reveals toxic and harmful; Super oxidation is high to equipment requirements, so cost is high, and operating risk is larger, is difficult to popularize.
Some Enterprises adopts activated sludge process to process Paraquat waste water (Zhang Yongmei, etc.), approximately 2000 yuan/waste water of estimated cost in conjunction with burning method; Also have enterprise to adopt catalytic oxidation (CN 1576242A), in waste water, add catalyzer, under 100-200 ℃, the condition of 0.9-1.5MPa, react 12-24 hour, COD clearance is higher than 90%, and cyanogen root is almost removed completely, and the clearance of colourity has also surpassed 90%, biochemistry pool can be directly entered in water outlet, but the required pressure of this technique is large, the reaction times is longer, high cost, is not suitable for the continous way industrial wastewater treatment system of Ji compare large enterprises of medium and small sized enterprises; Patent CN 101628767A has delivered a kind of technique that reclaims successively Paraquat, cyanogen root, ammonium salt, with extraction process, reclaim Paraquat, with alkaline emulsion, absorb cyanogen root, again the waste water two effect evaporations except after cyanogen are obtained to ammonium salt, this technique has reclaimed most of objectionable impurities, but removal process complicated operation, required medicament kind is many and price is higher, and more difficult automatic management and cost are higher; The people such as Fu Guanglong published an article in 2012, used TiO 2/ flyash is worked in coordination with Fenton agent treated Paraquat waste water, TiO 2/ fine coal preparation method of reagent thereof is complicated, high cost, is difficult to promote.
Summary of the invention
In Paraquat production process, produce a large amount of high chromas, high COD, high ammonia nitrogen and highly toxic toxic wastewater, do not have now general, economically viable treatment process, it is main art breading Paraquat waste water that the present invention takes ozone oxidation → condensing crystal → wash, and take ozone oxidation and process this waste water as main method, flow process is brief, simple to operate, can obtain with lower cost recovery purer chlorination ammonium salt and other can reuse product, obtain that product is qualified and to produce solid waste amount little, compare existing technique, this technique is easy to operate, cost is low, be more suitable for the enterprise in medium and small sized enterprises and transitional period.
For achieving the above object, the technical scheme that the present invention takes is as follows:
A treatment process for Paraquat agricultural chemicals waste water, serves as theme with " ozone oxidation → condensing crystal → washing ", and concrete steps are as follows:
(1) ozone oxidation: to the waste water of collecting, add sorbent material and hydrogen peroxide, and the decolouring of logical ozone oxidation; In ozone oxidation process, with hydrochloric acid or ammoniacal liquor, control the pH reacting and remain on 5-7.
(2) filter: in the solution after processing to step 1), add a small amount of hydrogen peroxide, slightly mix rear direct filtration.
(3) concentrated: the filtrate condensing crystal obtaining step 2);
(4) desalinization of soil by flooding or leaching: concentrated solution separating step 3) obtains slightly colored salt, adds saturated salt solution washing 1-5 time, filters and obtains cleaner salt.
Further improve above-mentioned technique, obtain following:
In step (1), hydrogen peroxide mass concentration is 50%, and the 0.01-10% that dosage is wastewater quality plays the effect of catalyzed oxidation, for strengthening the oxygenizement of ozone; The dosage of sorbent material is the 0.1-5% of wastewater quality.More preferred, the ozone flow passing into is 30-90g/h; Sorbent material is a kind of in aluminum oxide, gac, molecular sieve, diatomite, flyash; The addition of hydrogen peroxide is the 0.5-3% of wastewater quality, and system pH regulates and controls by hydrochloric acid or ammoniacal liquor, and pH is controlled at 6-8.
In step (2), it is 30% hydrogen peroxide that the solution after ozone oxidation need continue to add mass concentration, and the 0.01-2% that the addition of hydrogen peroxide is wastewater quality, for stable ozone oxidation effectiveness, prevents that solution colour from deepening.The 0.05-0.5% more preferred, the addition of hydrogen peroxide is wastewater quality.
In step (3), concentrated adopt MVR evaporation concentration, single-action is concentrated or Multi-effect concentration in a kind of or its combination; Concentrated gained condensation hot water is as washing water, recirculated water, product supplementary feed or in line and middle water reuse, and evaporation gained neatly can be used as cyclic steam heating and uses.
In step (4), the desalinization of soil by flooding or leaching adopts saturated ammonium chloride solution washing, the 10-50% that washing consumption is wastewater quality, and washing times is 1-5 time, and cycle index is 1-5 time, and the washes after recycling is back to step (3) evaporation concentration system and carries out salt manufacturing.
Paraquat agricultural chemicals waste water not only has high COD, high NH 3the features such as-N, but also contain a large amount of hypertoxic prussiates, adopt technique scheme of the present invention, its treating processes comprises " ozone oxidation → concentrated → desalinization of soil by flooding or leaching ", can obtain and meet clean recovery salt ammonium chloride, the ammonium chloride that separation is obtained is back to use in industrial production after being dried, and distillation water outlet and water coolant are back to use in production, the heat energy of collecting also can be used as produces energy use, and washes can continue salt manufacturing.In above-mentioned wastewater treatment process, can obtain the multiple energy can be recycled, significantly save processing cost, economic environmental protection, its principle of work and beneficial effect are as follows:
1. reclaim in salt-making process, using hydrogen peroxide as catalyzer, have the advantages such as green, environmental protection, easy recovery, and in reaction process, can not introduce the difficult ions of removing such as metal ion, do not use noble metal catalyst in whole reaction process, cost is lower;
2. recycling process is processed in normal pressure process, therefore, does not need the complex conditions such as High Temperature High Pressure in reaction process, and more for convenience, it is more convenient to operate for technology controlling and process.
3. in the above-mentioned treating processes of the present invention, the catalyzer hydrogen peroxide adopting has certain oxidation-reduction quality, in neutrality or alkaline waste water system, is not only conducive to strengthen the oxygenizement of ozone, promotes reaction to carry out, and improves effluent quality; And, because mostly waste water is to be exposed in outdoor environment, after ozone Oxidation Treatment, excessive hydrogen peroxide is conducive to the maintenance of oxidation effectiveness and stablizes, and has guaranteed maintaining for the treatment of effect, and water treatment effect is better, and inorganic salt quality improves.
4. in technique provided by the present invention, in reaction process, can not introduce the difficult ions of removing such as new metal ion, the catalyzer hydrogen peroxide adding is after completion of the reaction, can discharge with forms such as filtrate or distillates, therefore,, in whole reaction process, produce hardly solid waste amount, avoided wastewater treatment the generation in secondary pollution sources such as waste residue therefore, processing cost is low.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1
(COD=65200 mg/ L, NH3-N content is 89930 mg/ L to Paraquat agricultural chemicals waste water, CN -content=1100 mg/ L, pH=10-12), the salt acid for adjusting pH that adds mass concentration and be 36-38 % is 10, add wastewater quality 5 % gacs, logical ozone oxidation reaction, after 2 hours, adds the hydrogen peroxide (mass concentration is 50 %) of wastewater quality 10 %, continues oxidation 6 hours.On-line control pH in reaction process, the system pH of making is stabilized in 9 left and right.In waste water after oxidation finishes, add at once 2% hydrogen peroxide (mass concentration is 30 %) and be uniformly mixed 0.5 hour.The filtrate that filtration obtains is limpid lightcoral, records liquor C OD clearance approximately 75 %.By filtrate condensing crystal, obtain slightly yellowy salt, by the saturated washing lotion of 20 %, wash one time, obtain qualified Industrial Salt.The concentrated phlegma obtaining is as clear as crystal, COD=80 mg/L after measured, and ammonia nitrogen is greater than 1000 mg/ L.
Embodiment 2
In the present embodiment, (COD=65200 mg/ L, NH3-N content is 89930 mg/ L to Paraquat waste water, CN -content=1100mg/L, pH=10-12) add hydrochloric acid (36-38%wt) and regulate pH to be about 5, add the diatomite of wastewater quality 5%, all the other processing modes are identical with embodiment 1.Waste water after oxide treatment obtains limpid reddish-brown filtrate after filtration, and liquor C OD clearance is 57 %; By filtrate condensing crystal, obtain bolarious salt, the saturated solution washing with 30% 2 times, can obtain qualified Industrial Salt; The concentrated phlegma obtaining is limpid slightly red, records COD=340 mg/ L, and ammonia nitrogen is less than 35 mg/ L.
Embodiment 3
In the present embodiment, (COD=65200 mg/ L, NH3-N content is 89930 mg/ L to Paraquat waste water, CN -content=1100mg/L, pH=10-12) add hydrochloric acid (36-38%wt) and regulate pH to be about 7, add the gac of wastewater quality 0.1%, all the other processing modes are identical with embodiment 1.Waste water after oxidation finishes obtains limpid dark red filtrate after filtration, and liquor C OD clearance is 66 %.Filtrate condensing crystal, obtains pinkish-grey salt, and the saturated solution washing with 40% 2 times, can obtain qualified Industrial Salt.The concentrated phlegma obtaining is limpid slightly yellow, records COD=80 mg/ L, ammonia nitrogen approximately 100 mg/ L.
Embodiment 4
In the present embodiment, (COD=65200 mg/ L, NH3-N content is 89930 mg/ L to Paraquat waste water, CN -content=1100mg/L, pH=10-12) add hydrochloric acid (36-38%wt) and regulate pH to be about 7, add the gac of wastewater quality 5%, logical ozone oxidation reaction is after 2 hours, the hydrogen peroxide (mass concentration 50%) that adds wastewater quality 2%, continues oxidation 6 hours, and all the other processing modes are identical with embodiment 1.Oxide treatment waste water later obtains red filtrate after filtration, and liquor C OD clearance is 60 %; Filtrate condensing crystal, obtains ruddy salt, with the saturated solution of 25 %, washs 2 times, can obtain qualified Industrial Salt; The concentrated phlegma obtaining is limpid slightly yellow, records COD=282 mg/ L, ammonia nitrogen approximately 100 mg/ L.
Embodiment 5
Setting in the present embodiment is identical with embodiment 1, and difference is: (COD=65200 mg/ L, NH3-N content is 89930 mg/ L to Paraquat waste water, CN -content=1100mg/L, pH=10-12) add hydrochloric acid (36-38%wt) and regulate pH to be about 7, add the gac of wastewater quality 5%, logical ozone oxidation reaction, after 2 hours, adds the hydrogen peroxide (mass concentration is 50 %) of wastewater quality 2 %, continues oxidation 6 hours.Oxide treatment waste water direct filtration later, obtains limpid light red filtrate, and liquor C OD clearance is 69%; Filtrate is exposed in air after 24 hours, filtrate color becomes dark red, and COD slightly raises, and by filtrate condensing crystal, obtains pinkish-grey salt, with the saturated solution of 35 %, washs 2 times, can obtain qualified Industrial Salt; The concentrated phlegma obtaining is limpid slightly yellow, records COD=62 mg/ L, ammonia nitrogen approximately 100 mg/ L.
Embodiment 6
(COD=65200 mg/ L, NH3-N content is 89930 mg/ L to Paraquat agricultural chemicals waste water, CN -content=1100 mg/ L, pH=11) adding mass concentration is that the salt acid for adjusting pH of 36-38 % is 7, add Paraquat agricultural chemicals waste water total mass 0.5 % gac, logical ozone oxidation reaction is after 1 hour, the hydrogen peroxide (mass concentration is 50 %) that adds Paraquat agricultural chemicals waste water total mass 2.5 %, continue oxidation 3 hours, on-line control pH in reaction process, the system pH of making is stabilized in 7 left and right; In waste water after oxidation finishes, add at once the hydrogen peroxide (mass concentration is 30 %) of 0.5 % and be uniformly mixed 0.2 hour; The filtrate that filtration obtains is limpid redness, records liquor C OD clearance approximately 65 %; By filtrate condensing crystal, obtain slightly yellowy salt, the saturated salt solution washing with 20% 2 times, obtains qualified Industrial Salt; The concentrated phlegma obtaining is as clear as crystal, COD=75mg/L after measured, ammonia nitrogen 83 mg/ L.
Embodiment 7
(COD=17200 mg/ L, NH3-N content is 18700 mg/ L to Paraquat agricultural chemicals waste water, CN -content=540 mg/ L, pH=10) adding mass concentration is that the salt acid for adjusting pH of 36-38 % is 7, add Paraquat agricultural chemicals waste water total mass 0.2 % gac, logical ozone oxidation reaction is after 1 hour, the hydrogen peroxide (mass concentration is 50 %) that adds Paraquat agricultural chemicals waste water total mass 1 %, continue oxidation 2 hours, on-line control pH in reaction process, the system pH of making is stabilized in 7 left and right; In waste water after oxidation finishes, add at once the hydrogen peroxide (mass concentration is 30 %) of 0.1 % and be uniformly mixed 0.1 hour; The filtrate that filtration obtains is limpid redness, records liquor C OD clearance approximately 85 %; By filtrate condensing crystal, obtain slightly yellowy salt, the saturated salt solution washing with 10% 1 time, obtains qualified Industrial Salt; The concentrated phlegma obtaining is as clear as crystal, COD=25mg/L after measured, ammonia nitrogen 46 mg/ L.
Comparative example 8
(COD=65200 mg/ L, NH3-N content is 89930 mg/ L to Paraquat waste water, CN -content=1100 mg/ L, pH=10-12) add after the ferrous sulfate of wastewater quality 2 % and the hydrogen peroxide of wastewater quality 3 % (mass concentration is 50 %), add hydrochloric acid (mass concentration 36-38 %) to regulate pH to 5, be heated to 50 ℃ of left and right insulated and stirred reactions after 1 hour, in this solution, add the gac of 0.5 %, continue stirring reaction 1 hour, filter.Record COD clearance approximately 45 %, color removal approximately 50 %, CN -clearance approximately 85 %.Filtrate condensing crystal, separation obtains chlorination ammonium salt, and color is darker, dissolves after washing, then add mother liquor waste water 20 % Water dissolve salt recrystallization with the wash water of mother liquor waste water 20 %, and separation obtains cleaner chlorination ammonium salt.The concentrated phlegma obtaining is light yellow, and COD=850 mg/ L must further process after measured.
In table 1, provide and in embodiment, reclaim the quality of ammonium chloride and the contrast situation of industrial ammonium chloride quality standard, canonical reference GB/T 2946-2008.
The treatment effect synopsis that the different embodiment of table 1 obtains
Remarks: in table, "-" represents not detect.
In above-mentioned seven embodiment, the embodiment that embodiment 1-6 is technical solution of the present invention, comparative example 7 is conventional process mode.
From embodiment 1-6, can find out, after pH, catalyst levels, sorbent material consumption, reaction, the consumption of hydrogen peroxide all has obvious impact to water treatment effect: alkaline condition oxidation efficiency is high, and the loss of acidic conditions ammonium salt is little; Increase sorbent material consumption and can reduce inorganic salt bath water amount; Increase catalyst levels, can improve waste water COD clearance, reduce water of condensation COD; After oxidation, add hydrogen peroxide, can reduce inorganic salt washing water consumption.Specifically,
By embodiment 1 and 2,3, can find out: hydrogen peroxide katalysis to ozone oxidation under weak basic condition is the strongest, and under alkaline condition, ammonia volatilizees in a large number, produce salt amount and decline, in water of condensation, ammonia nitrogen exceeds standard; And under acidic conditions, hydrogen peroxide catalytic efficiency obviously declines, but ammonium salt loss is little, and in condensation, ammonia-nitrogen content is low.
By embodiment 2 and 3, can find out: when not adding or add sorbent material less, the chroma removal rate of waste water obviously declines, cause water of condensation band color, inorganic salt washing water consumption increases.
By embodiment 2 and 4, can find out: when not adding or add less catalyzer hydrogen peroxide, ozone oxidation efficiency obviously reduces.
By embodiment 2 and 5, can find out: after oxidation, do not add or a small amount of 30% hydrogen peroxide, chroma in waste water can become greatly gradually, cause inorganic salt washing water consumption to increase.
Comprehensive embodiment 1-6, can find out, in embodiment 6, after pH, catalyst levels, sorbent material consumption, reaction, the consumption of hydrogen peroxide reaches optimization, in this condition, not only keep waste water treatment efficiency high, phlegma is colourless, ammonia nitrogen is low, and inorganic salt bath water amount is few, also reduces various dosings, reduce medicament waste, reduce process costs.
Comparative example 6 and embodiment 7, can find out, ozone oxidation is more obvious to low concentration wastewater effect.
Compare the conventional process mode described in embodiment 8, technical scheme provided by the present invention has advantage in following several respects:
First, scheme operation provided by the present invention is terse, and traditional way treatment process is many, and the pharmaceutical agent of consumption is more.In traditional way, except the operations such as deoxidation, also need to carry out insulation reaction, recrystallization reaction just can complete the processing of Paraquat agricultural chemicals waste water, and it processes condensed waste water also needs to carry out advanced treatment and just can reach discharge standard, and in the scheme that the application provides, pass through ozone oxidation, filter, concentrated, the desalinization of soil by flooding or leaching, operation is terse, in treating processes, without consuming a large amount of heats, carry out insulation reaction, also need not adopt the operations such as recrystallization and advanced treatment, can reach in line standard, processing efficiency is very high, the electric energy consuming in treating processes, heat energy, resources etc. are all less, for energy-saving and emission-reduction, be also highly beneficial.
Secondly, from treatment effect, the chroma in waste water after the present invention processes reduces obviously, and COD reduced rate is far away higher than the effect of comparative example.Waste water after the present invention processes, its colourity is less, COD reduced rate can reach more than 65%, and in comparative example, waste water color and luster after processing is still darker, COD clearance only can reach 50% left and right, and the waste water after processing also needs to carry out the operations such as recrystallization, advanced treatment, and the waste water after processing cannot carry out in line.
Finally, from reclaiming product quality aspect, in the product that scheme provided by the present invention reclaims, can not introduce new impurity, and heavy metal content is low.Because each parameter in embodiment 6 reaches optimization, based on this, table 1 only contrasts with the recovery product that comparative example 7 obtains embodiment 6, as can be seen from Table 1: the quality of embodiment 6 gained ammonium chlorides reaches industrial standards premium grads rank, and the quality of comparative example's 7 gained ammonium chlorides only can reach industrial standards first grade rank; In processing condition provided by the present invention, do not use the medicine containing other metal ions, therefore reclaim in product chlorination ammonium salt and do not detect and tap a blast furnace, and in traditional technology, adopt iron content medicament, in its output ammonium chloride, can contain a certain amount of iron that cannot reclaim or remove; Containing sulfate hardly in conventional Paraquat agricultural chemicals waste water to be processed, in technique of the present invention, do not use vitriol yet, therefore containing sulfate not in the ammonium chloride of output, and containing sulfate in the Fenton reagent that traditional method is used, in product after processing, not only cannot remove metallic iron ion, also additionally bring newly-increased sulfur impurity hydrochlorate into; In the technique that embodiment 6 adopts, do not add or produce any high boiling point insoluble impurity, so its ignition residue amount is little, product solid waste after subsequent disposal is less, and in embodiment 7, introduced this type of more impurity, its ignition residue amount is relatively high, has also increased accordingly post-processing difficulty.
The comprehensive the various embodiments described above of analyzing, guaranteeing under the good prerequisite of output inorganic salt product quality, To Several Traditional Preconditioning Methods not only can be introduced a large amount of impurity, also need heating and thermal insulation reaction, and the removal effect of chroma in waste water and COD is starkly lower than to technique of the present invention, cause the salt after concentrating by simply washing is up to standard, still to need recrystallization; Meanwhile, not only COD is high for the water of condensation that condensing crystal produces, and colourity is higher, cannot directly utilize, and needs advanced treatment.Compare with technique of the present invention, not only weak effect, and treatment condition is more complicated, and cost is high, recrystallization especially, and its cost seriously limits the application of traditional method in middle-size and small-size factory.And in the technical solution used in the present invention, by ozone oxidation, filtration, the efficient processing that concentrated, the desalinization of soil by flooding or leaching can realize waste water, and the preparation cost of the ozone using decreases, by ozone Oxidation Treatment with other modes are combined, while being applied to Paraquat wastewater treatment, not only can reach efficient treatment effect, waste water COD is obviously reduced, and waste water color and luster is down to can emission standard, and cost is lower, technique is more succinct, better effects if.

Claims (5)

1. the treatment process of a Paraquat agricultural chemicals waste water, it is characterized in that comprising the steps: (1) ozone oxidation: to the sorbent material that adds wastewater quality 0.1-5% in the waste water of collecting, hierarchy of control pH is at 5-9, pass into after ozone Oxidation Treatment 1-4 hour, the hydrogen peroxide that adds wastewater quality 0.01-10%, hydrogen peroxide concentration is 50-70%, continues oxidation 1-10 hour; (2) filter: the hydrogen peroxide to again adding wastewater quality 0.01-2%, mass concentration 30% in the waste water after step (1) oxide treatment, stirs filtration after 0.1-1 hour; (3) condensing crystal: the filtrate after step (2) is filtered is carried out after condensing crystal, and separation obtains crystal salt; (4) desalinization of soil by flooding or leaching: adopt saturated salt solution to wash 1-5 time the crystal salt of step (3), cycle index is 1-5 time, saturated salt solution consumption by the 10-50% of processing waste water total mass, filter and obtain finished product, washes again reuse to condensing crystal carry out recovery and the purifying of finished product salt.
2. the treatment process of a kind of Paraquat agricultural chemicals waste water as claimed in claim 1, is characterized in that: described sorbent material is a kind of or its mixture in aluminum oxide, gac, molecular sieve, diatomite, flyash.
3. the treatment process of a kind of Paraquat agricultural chemicals waste water as claimed in claim 1, is characterized in that: in step (1), ozone flow is 30-90g/h; The addition of hydrogen peroxide is the 0.5-3% of wastewater quality, and system pH regulates and controls to 6-8 by hydrochloric acid or ammoniacal liquor.
4. the treatment process of a kind of Paraquat agricultural chemicals waste water as claimed in claim 1, is characterized in that: in step (2), and the 0.05-0.5% that the addition of hydrogen peroxide is wastewater quality.
5. the treatment process of a kind of Paraquat agricultural chemicals waste water as claimed in claim 1, it is characterized in that: in step (3), condensing crystal refers to one or more the combination in the concentrated or Multi-effect concentration of MVR evaporation concentration, single-action, and saturated salt solution is saturated ammonium chloride solution.
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CN109848185A (en) * 2019-03-11 2019-06-07 安徽华星化工有限公司 A kind of harmless processing method of Cupric sulfate abraum salt
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CN110981013A (en) * 2019-12-16 2020-04-10 江苏兄弟维生素有限公司 Method for treating waste liquid after extraction of thiamine

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