CN102344213A - Treatment process for calcium hypochlorite secondary mother liquor wastewater and treatment agent thereof - Google Patents
Treatment process for calcium hypochlorite secondary mother liquor wastewater and treatment agent thereof Download PDFInfo
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- CN102344213A CN102344213A CN2011101893819A CN201110189381A CN102344213A CN 102344213 A CN102344213 A CN 102344213A CN 2011101893819 A CN2011101893819 A CN 2011101893819A CN 201110189381 A CN201110189381 A CN 201110189381A CN 102344213 A CN102344213 A CN 102344213A
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Abstract
The invention provides a treatment process for calcium hypochlorite secondary mother liquor wastewater and a treatment agent thereof. The treatment process is a new process for treating the calcium hypochlorite secondary mother liquor wastewater by applying industrial waste residue fly ash as a water treatment agent. The treatment process comprises the following steps of: firstly separating high-concentration residue slurry from the calcium hypochlorite secondary mother liquor wastewater under the force of gravity, centrifugally separating after the supernatant fluid of the high-concentration residue slurry is mixed with the water treatment agent and discharging separated clear water in a manner of reaching the standard through adjusting the pH value of the supernatant fluid by industrial hydrochloric acid; and discharging the residue slurry after being subjected to harmless treatment. With the adoption of the treatment process, wastes be treated with wastes, and not only can the color of the waste water be effectively reduced, and can the concentration of suspended matters reach the requirements of the national emission standard (GB8978-1996), but also the pH value of the wastewater can be adjusted. Through executing the treatment process, not only can the discharge of pollutants be reduced, but also the level of the circular economy of an enterprise can be improved so as to conform to the requirements for national low carbon economy.
Description
Technical field
What the present invention relates to is the method for wastewater treatment, the particularly treatment process of high test bleaching powder secondary mother liquid waste water and treatment agent thereof during high test bleaching powder is produced.
Background technology
High test bleaching powder is good bleaching and disinfecting agents; The available chlorine content of its main component Losantin is up to more than 70 %; Have easy to use, stable performance, be convenient to advantages such as transportation and storage, be widely used in sterilization, the sterilization of aspects such as chemical industry, light industry, food sanitation and daily life, production.1 ton of high test bleaching powder of average in process of production every production just has mother liquor of 5 tons of high test bleaching powders to produce.This mother liquor generally can get into original production process utilization once more; But the secondary mother liquid waste water that after recycle, produces still contains available chlorine 1.9-2.5%; Color is light red to piece redness; Contain the cotton-shaped suspended substance of a large amount of whites, its major ingredient is Losantin, calcium hydroxide, lime carbonate.Reclaim difficulty again owing to available chlorine content in the secondary mother liquid waste water is low, usually direct waste discharge causes serious pollution to ambient water quality.
At present, the available technology adopting membrane filter method recycles secondary mother liquid waste water.Make secondary mother liquid pass through membrane filtration wherein slaked lime and available chlorine is further reclaimed, filter the back water outlet and efflux.This method can the recovery part starting material, reduce concentration of suspension in the waste water, bring certain economic return, but reclaim the requirement that colourity, pH value and the concentration of suspension of back waste water still do not reach " integrated wastewater discharge standard GB8978-1996 ".And with high test bleaching powder secondary mother liquid waste water inorganic or organic membrane filter method processing high suspended matter concentration; Owing to the strong oxidizing property and the strong basicity of waste water is easy to cause the damage of organic membrane to need frequent change; And mineral membrane is easy to take place dirty blocking up in actual motion; Equipment life is shorter, and the liquid waste disposal facility can't normally move.Therefore, with inorganic or organic membrane filter method secondary mother liquid waste water being recycled still can not qualified discharge.
High test bleaching powder factory effluent or waste liquid have characteristics such as strong oxidizing property, severe corrosive, strong basicity, high suspended matter, high chroma, high saliferous; Not only the harm to environment is big for it; Intractability is also very big; Conventional treatment technology does not have removal effect basically to its pollutent, and at present domestic qualified discharge rate is very low.
Summary of the invention
The objective of the invention is to propose a kind of applicable industry waste residue and pulverized fuel ash is handled high test bleaching powder secondary mother liquid waste water as water conditioner novel process.This technology can the treatment of wastes with processes of wastes against one another, not only can effectively reduce the colourity of waste water, the concentration of suspended substance reaches the requirement of discharging standards, can also adjust the pH value of waste water.The enforcement of technology both can reduce the discharging of pollutent, also can promote the level of enterprise's recycling economy, met the requirement of national low-carbon economy.
The present invention realizes like this; Its technical process is shown in Figure of description; Wherein in the reaction tank supernatant liquor, adding treatment agent is a kind of industrial residue; Composition is flyash (deriving from the coal dust waste residue of the boilers such as thermal power plant, heat power plant and concentrated supply of heating in the city that are fuel); Add-on is 0.5～2%; In the neutralization tank supernatant liquor, adding the reductive agent composition is S-WAT, and add-on is 1.5～2.5% (above all be weight percentage, below identical).
Stir 15-60min after in the reaction tank supernatant liquor, adding the flyash treatment agent, in neutralization tank,, it is adjusted to pH8-9 with the pH value of technical hydrochloric acid adjustment supernatant liquor.
After in deslagging jar sediment, adding the 10-20% clear water, add 2% reductive agent, stirred 15-60 minute.
The operational path brief introduction
High test bleaching powder secondary mother liquid waste water is transported to vertical-flow slurry tank through storage tank by lift pump, and waste water carries out preliminary solid-liquid separation at this.The purpose that slurry tank is set is to remove solid pollutants such as lime carbonate in the waste water, calcium hydroxide, Losantin, the dosage of medicament when reducing wastewater treatment.The gravity flow of slurry tank supernatant liquor gets into the waste water reaction pond; In the waste water reaction pond, add treatment agent flyash; After in reaction tank, mixing reaction 15-60min; Be transported to whizzer A by pneumatic diaphragm pump and carry out solid-liquid separation (separating factor is greater than 3000); The centrifugation water outlet is to neutralization tank; Through adding hydrochloric acid adjustment pH value behind 8-9, water quality reaches " integrated wastewater discharge standard " (GB8978-1996) first discharge standard requirement.Eliminate qualified discharge behind the free chlorine through adding reductive agent again in the neutralization tank waste water.The isolated sediment of whizzer A gets into the deslagging jar.If need not to remove reactive chlorine, the processing step that adds reductive agent elimination free chlorine can save.
Enter high density in the slurry tank bucket white slag slurry every day slag slurry jar for 1 time, be transported to whizzer B through pneumatic diaphragm pump and carry out further solid-liquid separation; The isolated waste water of whizzer B gets into reaction tank, gets into Waste Water Treatment and handles.The sediment that whizzer B discharges gets into the deslagging jar, if the sediment that whizzer B discharges reaches the requirement of raw materials for production, then can return production line and utilize.
All get into the sediment of deslagging jar, add reductive agent S-WAT and less water and mix, and redox reaction takes place thoroughly remove reactive chlorine.Harmless treatment is sent to the cement mill cement baking later on or is removed the household refuse landfill sites landfill, and all solids waste of generation is eliminated fully.
The characteristics of technical process of the present invention:
(1) adopt a kind of industrial residue flyash to purify liquid waste, the thermoelectric plant of this enterprises of high test bleaching powder that can have drawn from, this expense are zero, and for the flyash waste residue provides new recycling approach, the treatment of wastes with processes of wastes against one another meets circular economy concept.This technology flyash is adding less, and chromaticity removing effect is fine, can reach the primary standard in the integrated wastewater discharge standard.
(2) adopt gravity separation to go out the mentality of designing that supernatant liquor and lower floor's emulsion are handled respectively again, contaminant removal efficiency is compared raising greatly with direct dispensing.Technology is stable, and water outlet is effective.Two seasons of summer in winter can reach emission standard.
(3) the waste residue amount of centrifugal generation is few, and can be utilized again.Calculate with 100 tons/d secondary mother liquid wastewater treatment capacity; Through solid-liquid separation with add reductive agent, produce 2 tons in the innoxious waste residue that does not contain reactive chlorine, water ratio 20-30%; Plastic stacking, be transported to the cement mill cement baking or send to household refuse landfill sites, all contaminants is eliminated fully.
(4) Shai Xuan S-WAT reductive agent is good to waste residue dechlorination treatment effect, and the reaction times is short, and processing costs is low.Solved the problem of outlet that contains the reactive chlorine waste residue.
(5), carried out lab scale research as tachnical storage, and on technology, done reservation to temporarily there not being this contamination index of reactive chlorine of limit value in the present national sewage comprehensive emission standard.
(6) this process treatment process safety.Dosing processing and solid-liquid separation process do not produce chlorine.Reactive chlorine only has few part natural decomposition in water to overflow, and can eliminate the influence of waste gas to operator and surrounding enviroment through exhaust-gas treatment facilities is set.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
In the laboratory, high test bleaching powder secondary mother liquid waste water is carried out water quality and proximate analysis.The result sees table 1 and table 2.High test bleaching powder secondary mother liquid waste water water sample outward appearance is the suspension liquid that rose contains the white suspension thing.After leaving standstill 0.5h, the thick white depositions of 2cm appears in the bottom, and the upper strata is pink clear liquid, and irritating smell is arranged.Can be known that by table 1 and table 2 water quality characteristics of high test bleaching powder secondary mother liquid waste water is: suspended substance, colourity and pH value exceed standard seriously.Colourity exceeds standard 5 times, and suspended substance exceeds standard 9 times.Wherein suspended substance contains water-fast CaCO3, is slightly soluble in the Ca (OH) of water
2And Ca (ClO)
2
Table 1. secondary mother liquid waste water quality analytical results
The contained component of table 2. secondary mother liquid waste water
Embodiment 1The purifying treatment of supernatant liquor after the gravity separation
5 liters of high test bleaching powder secondary mother liquid waste water in the container are left standstill 1h～2h, supernatant liquor is slowly poured in the clean beaker, can slowly topple over the powder rose supernatant liquor that 3.5L, remaining 1.5 are upgraded to high concentration powder white emulsion.
(1) flyash dosage and decolorizing effect test
Surveying supernatant liquor colourity is 512 times, and pH is 10.52, surpasses emission standard.Concentration of suspension is very low, is 10.5mg/L, reaches emission standard.Therefore the difficult point of supernatant liquor improvement is decoloured exactly.
Adopt treatment agent flyash to the supernatant liquor processing of decolouring.Get 4 in beaker, each adds supernatant liquor 100mL, adds the flyash of 0.1g, 0.25g, 0.5g, 1g, 1.5g, 2g gram respectively.After stirring 3～6min on the magnetic stirring apparatus, mixed solution is put into whizzer respectively carry out centrifugation.Centrifugation time 5min.Measure the colourity of supernatant liquor respectively and see table 3.
The decolorizing effect (former colourity 512 times) of table 3. flyash under different dosages
Can know that from table 3 flyash has good effect to the removal of colourity.At dosage is 0. 25% o'clock, and effluent color dilution can reach the secondary standard in the integrated wastewater discharge standard, is that 0.5% effluent color dilution when above can reach the primary standard in the integrated wastewater discharge standard at dosage.
Its reaction principle is: when adding the flyash treatment agent, because the insatiable hunger property of its surperficial valence link and have a large amount of oxy radicals, reaction and surface physics adsorptions such as oxidation, complexing and galvanic deposit take place in water-soluble back, and colourity is descended.
(2) best churning time confirms
Get 4 beakers, each adds the supernatant liquor of 100mL, and each adds flyash 0.5%, stirs with the magnetic stirring apparatus middling speed, and churning time is respectively 0.5min, 1 min, 3 min, 6 min, 15min, do centrifugation after, measure the supernatant liquor colourimetric number and see table 4.
The different churning time of table 4. are to the influence of chromaticity removing effect
Known that by table 4 when one timing of treatment agent add-on, churning time is long more, centrifugal rear decoloring effect is good more.Along with the increase of churning time, the value increase trend of chroma removal rate tends towards stability.Take all factors into consideration, get churning time 3-6min.It is 0.5～1h that main equipment is got churning time.
(3) optimal reaction temperature confirms
Measure 26.8 ℃ of room temperatures.Get 4 in beaker; Respectively pour the 150mL water sample into; Be placed on three JB-L type constant temperature blender with magnetic force after adding flyash 0.5% respectively; Temperature is set to room temperature respectively, 40 ℃ and 50 ℃, puts cold compartment of refrigerator temperature in period earlier at 0-4 ℃ of degree for the 4th; When temperature reaches design temperature; Begin simultaneously to stir, rotating speed is identical, and churning time is 6min.Carry out centrifugation then, its decolorizing effect is seen table 5.
The different wastewater temperatures of table 5. are to the influence of chromaticity removing effect
When wastewater temperature was 26.8 ℃, decolorizing effect was best, and along with the rising and the reduction of temperature, decolorizing effect has the trend of variation.But still can reach the water quality emission standard, so the present invention does not establish temperature requirement.
(4) medicament of adjust pH is selected
Supernatant liquor is respectively got 100mL puts into two beakers, respectively with dilute hydrochloric acid and dilute sulphuric acid adjustment pH value to 8-9, leave standstill 0.5 hour after, observe.Find to add the complete clear, colorless of clear liquid in the beaker of hydrochloric acid, have only the trickle white suspension thing of minute quantity, on the sense organ near tap water.The supernatant liquor that adds dilute sulphuric acid is colourless, but a small amount of white suspension thing is arranged, and the calcium sulfate that is slightly soluble in water for calcium ion in the water and sulfate radical reaction generation causes the water quality transparency to descend.
According to test, confirm to use the pH value of dilute hydrochloric acid adjustment supernatant liquor, adjust in the scope of 8-9 and get final product standard discharge.
(5)To reactive chlorine degradation treatment in the supernatant liquor
Reactive chlorine in the supernatant liquor of decolouring back on average is about 1.7%; China's integrated wastewater discharge standard does not have limit value to reactive chlorine in the high test bleaching powder waste water at present; The present invention has increased removing the step of reactive chlorine in the water; Be intended to the removal method is carried out tachnical storage and technology reservation; In case qualified discharge can be accomplished after the reactive chlorine index in the high test bleaching powder waste water is had requirement immediately by country.
Select for use the reductive agent S-WAT to the test of degrading of reactive chlorine in the water.
Testing sequence: get decolouring back supernatant liquor, press the S-WAT that reaction ratio adds 1.5-2.5%, stir with glass rod and observe, do not have the generation of bubble and irritating smell in the reaction, adularescent flocks generation is measured wherein active chlorine content at different time and is seen table 6.
Table 6. decolouring back supernatant liquor adds behind the reductive agent reactive chlorine with the variation in reaction times
After adding reductive agent S-WAT 15min, the reactive chlorine clearance is a clearance 52.1% after 18.2%, 4 hour, and clearance is up to 94.8% behind the 8h.Its principle is: S-WAT and the hypochlorite generation redox reaction with strong oxidizing property are reduced into chlorion with hypochlorite.
Embodiment 2.Processing to high density slag slurry in bottom after the gravity separation
1.5 remaining rising concentration emulsion are the slag slurry that contains the outstanding absurd creature of a large amount of whites in the foregoing description 1.Slag is starched the back that stirs take out 100mL, the back of weighing adopts the laboratory to carry out centrifugation with supercentrifuge.Rotating speed 4000～7000 commentaries on classics/min, disengaging time are 5min.Separate the back and measure the quality of clear liquid and the quality of sediment.The clear liquid that obtains after the separation is the pale pink transparent liquid, and lighter irritating smell is arranged, and can integrate with in the supernatant liquor that gravity separation obtains and handle together.The water ratio of measuring white sediment is 21%, can moulding stack and transportation.
The dreg slurry proximate analysis of table 7. 100mL
(1) with reductive agent the slag slurry is directly carried out the dechlorination test.
The secondary mother liquid natural sedimentation, lower floor's slag slurry obtains white sediment after centrifugation, contain 1.81% Losantin, if the direct continuous release chlorine of outer National Games causes environmental pollution and danger.Therefore must carry out harmless treatment transports outward disposal again.
Testing sequence: produce high density slag slurry 125.22g after getting gravity settling, directly add reductive agent 2.5g (weight percent 2%), stirred 5-15 minute and measured active chlorine content and see table 8.
Table 8. slag slurry adds behind the reductive agent reactive chlorine with the variation in reaction times
(2)With reductive agent the centrifugal back of slag slurry sediment is carried out the dechlorination test.
Testing sequence: carry out centrifugation to producing high density slag slurry behind the gravity settling, extracting waste paste sediment 4.8862g, add the 10-20% clear water after, add reductive agent 0.1g (weight percent 2%), stirred 5-15 minute and measured active chlorine content and fill in the table 9.Stirred 30-60 minute for main equipment.
Table 9. sediment adds behind the reductive agent reactive chlorine with the variation in reaction times
Know relatively that by table 8,9 the reductive agent S-WAT all has good removal effect to the reactive chlorine in high density slag slurry and the slag slurry dehydration back sediment.It is much faster than directly in high density slag slurry, directly adding reductive agent wherein in sediment, to add its reactive chlorine removal speed of reductive agent, and clearance just reaches 95.8% behind 60min.It is the slowest in the slag slurry, to remove reactive chlorine speed, and this maybe be relevant with the very high system complicacy of concentration of suspension in the slag slurry.Therefore remove reactive chlorine selecting to add reductive agent again after sloughing clear liquid on the technology to high density slag slurry is centrifugal.Because this reaction has water to participate in, so will in sloughing the sediment of clear liquid, add a small amount of clear water so that reaction is carried out smoothly fast.
On-the-spot natural evaporable chlorine contained exhaust gas can be eliminated the influence to operator and surrounding enviroment through exhaust-gas treatment facilities is set.
Claims (6)
1. the treatment process of a high test bleaching powder secondary mother liquid waste water is characterized in that its technical process is shown in Figure of description.
2. the treatment process of a kind of high test bleaching powder secondary mother liquid waste water according to claim 1 is characterized in that added treatment agent is a kind of industrial residue flyash in the reaction tank supernatant liquor, and add-on is 0.5～2%.
3. the treatment process of a kind of high test bleaching powder secondary mother liquid waste water according to claim 1 is characterized in that added reductive agent composition is a S-WAT in the neutralization tank supernatant liquor, and add-on is 1.5～2.5%.
4. the treatment process of a kind of high test bleaching powder secondary mother liquid waste water according to claim 1 stirs 15-60min after it is characterized in that in the reaction tank supernatant liquor, adding the flyash treatment agent.
5. the treatment process of a kind of high test bleaching powder secondary mother liquid waste water according to claim 1 is characterized in that with the pH value of technical hydrochloric acid adjustment supernatant liquor it being adjusted to pH8-9.
6. the treatment process of a kind of high test bleaching powder secondary mother liquid waste water according to claim 1, the treatment process of the waste residue that it is characterized in that producing, in deslagging jar sediment, add the 10-20% clear water after, add the reductive agent of weight percent 2%, stirred 30-60 minute.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818138A (en) * | 2019-11-22 | 2020-02-21 | 陕西北元化工集团股份有限公司 | Chlor-alkali wastewater treatment method |
| CN112340700A (en) * | 2020-12-02 | 2021-02-09 | 中国成达工程有限公司 | System and method for recycling chlorine from waste mother liquor of bleaching powder |
| CN113307316A (en) * | 2021-06-18 | 2021-08-27 | 中国人民解放军陆军防化学院 | Decontamination wastewater neutralization treatment composition and use method thereof |
| CN113402006A (en) * | 2021-06-18 | 2021-09-17 | 中国人民解放军陆军防化学院 | Efficient harmless treatment composition for decontamination wastewater and use method thereof |
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| CN101941755A (en) * | 2010-10-12 | 2011-01-12 | 南京工业大学 | Modified fly ash, preparation method thereof and method for treating humic acid |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101941755A (en) * | 2010-10-12 | 2011-01-12 | 南京工业大学 | Modified fly ash, preparation method thereof and method for treating humic acid |
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| 王秀平等: "漂粉精生产过程中副产废液的回收利用", 《氯碱工业》 * |
| 韩家俊等: "钠法漂粉精母液循环利用的中试研究", 《氯碱工业》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818138A (en) * | 2019-11-22 | 2020-02-21 | 陕西北元化工集团股份有限公司 | Chlor-alkali wastewater treatment method |
| CN112340700A (en) * | 2020-12-02 | 2021-02-09 | 中国成达工程有限公司 | System and method for recycling chlorine from waste mother liquor of bleaching powder |
| CN112340700B (en) * | 2020-12-02 | 2023-10-27 | 中国成达工程有限公司 | System and method for recycling chlorine from waste mother liquor of bleaching powder |
| CN113307316A (en) * | 2021-06-18 | 2021-08-27 | 中国人民解放军陆军防化学院 | Decontamination wastewater neutralization treatment composition and use method thereof |
| CN113402006A (en) * | 2021-06-18 | 2021-09-17 | 中国人民解放军陆军防化学院 | Efficient harmless treatment composition for decontamination wastewater and use method thereof |
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