CN101973659A - Device and method for refining waste water by treating vitamin B12 by means of co-use of micro-electrolysis and physicochemical method - Google Patents
Device and method for refining waste water by treating vitamin B12 by means of co-use of micro-electrolysis and physicochemical method Download PDFInfo
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- CN101973659A CN101973659A CN 201010513042 CN201010513042A CN101973659A CN 101973659 A CN101973659 A CN 101973659A CN 201010513042 CN201010513042 CN 201010513042 CN 201010513042 A CN201010513042 A CN 201010513042A CN 101973659 A CN101973659 A CN 101973659A
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Abstract
The invention belongs to the technical field of non-degradable waste water, and especially relates to a device and a process for refining waste water by treating vitamin B12 by means of co-use of micro-electrolysis and physicochemical method; the device is composed of a raw water tank, a micro electrolysis water supply pump, a micro electrolysis apparatus, a mixed water pond, a bentonite adding device, a bentonite preparing unit, a flocculating water tank, a coagulant adding device, a centrifugal water supply pump and a centrifugal separation apparatus; according to the invention, the content of non-degradable matters in waste water can be efficiently reduced by means of micro electrolysis, physicochemical treatment, flocculation and the treatment in a solid/liquid separation apparatus so as to enhance biodegradability of waste water, which is better favorable for subsequent biological treatment systems. After waste water is treated by micro-electrolysis-physicochemical method, the traditional biochemical treatment equipment at later stage has lower COD load and better treatment effect, and the project investment is low, the operation expenditure is acceptable. The device and the method according to the invention can be extensively applied to the treatment for industrial waste water in pharmacy, coking, agricultural chemical and other fields.
Description
Technical field
The invention belongs to the used water difficult to degradate processing technology field, relate in particular to the processing vitamins B of a kind of little electrolysis, physico-chemical process coupling
12The device and method of waste water.
Background technology
Vitamins B
12Factory effluent belongs to its CODcr of high concentration hard-degraded organic waste water can be up to 30,000 to 50,000 mg/L; BOD
5With the ratio of CODcr less than 0.3, be difficult to biological degradation; Because these characteristics tend to environment is caused severe contamination.
The pharmacy waste water pollutent has that content height, concentration of suspension are big, strong toxicity, hard-degraded substance is many, change of water quality is fast, water yield luffing greatly and characteristics such as processing complexity, all be the emphasis and the difficult point of Industrial Wastewater Treatment all the time.
Pharmacy waste water is handled and is generally adopted anaerobic biological to handle and the anaerobic-aerobic biochemistry combination process at present, but action of microorganisms such as inhibition even killing bacteria are arranged because of residual big measure feature pollutent in the waste water, poor processing effect not only, and cause migration and the enrichment of feature pollutent in ecology in the pharmacy waste water easily, form serious secondary pollution.Have simultaneously that investment is big, long processing period, be subjected to many shortcomings such as the big and result instability of seasonal effect.The high consumption of the complicacy of pharmacy waste water and routine biochemistry treatment process, inefficiencies are to cause current a large amount of pharmacy waste water to be difficult to handle and be difficult for up to standard.Vitamins B
12Waste water is rich in organic acid, protein, polysaccharide and other degradation productions, and complicated component has higher colourity, through the vitamins B of biological treatment processing
12Refinement waste water can not reach the requirement of qualified discharge, need carry out pre-treatment before biological treatment.Therefore, to vitamins B
12The Study on processing method of factory effluent has significant meaning.
Traditional biological treating equipment is handled vitamins B
12It is very undesirable to refine the waste water effect.So the pre-treatment measure that needs to be fit to ensures, because vitamins B
12Refine the waste water complicated component, and biodegradability is poor.Therefore its pre-treatment and auxiliary process adopt little electrolysis to add physico-chemical process and handle removal colourity and portion C OD
CrThe time improve biodegradability.
Fe-C Micro Electrolysis Method often is applied to the pretreatment stage that bio-refractory waste water (as trade effluents such as dyestuff, printing and dyeing, agricultural chemicals, pharmacy, chemical industry) is handled, chain rupture, color development and the auxochromes that this method can realize larger molecular organics because of decolouring, improve the biodegradability of waste water.
Little electrolytic oxidation reduction is to utilize when having high-valency metal certain specific surface, that contain a large amount of conductive impurities that the galvanic corrosion reaction takes place under sour environment, between metal and impurity, form microelectrode, separate and produce the active hydrogen of capacity by the microelectrode point, and utilize it to strengthen reductibility and decompose and reduce high-molecular-weight organic material.The redox potential of iron and carbon differs bigger, adds iron filings and iron carbon dust in waste water, forms corrosion cell thus.Its collection redox, flocculation absorption, catalyzed oxidation, complexing and galvanic deposit etc. act on one.Under acidic conditions, when being added to the iron carbon mixture in the electrolyte solution, can following electrode reaction take place by galvanic effect between the two:
Anode (Fe): Fe-2e → Fe2+, E
θ=-0.44V (1)
Negative electrode (C): 2H
++ 2e → 2[H] → H2, E
θ=0V (2)
The product that electrode reaction generates has higher chemically reactive.Concrete effect mainly contains:
(1) a large amount of status nascendi Fe that produce in new iron surface that produces and the reaction
2+Have high chemically reactive with atom H, can change many organic structures and characteristic in the waste water, make effects such as organism generation chain rupture, open loop;
(2) Fe of reaction generation
2+Participate in the redox reaction in the solution, generate Fe
3+Reaction later stage pH value of solution value raises Fe
3+Hydrolysis generates the big Fe (OH) of the polymerization degree gradually
3The colloid flocculation agent can adsorb, the pollutent in the water that flocculates effectively, thereby strengthens the decontamination effect improving to waste water.
Wilkinite (Bentonite) is the moisture clay pit based on montmorillonite, and chemical ingredients is: (Al
2, Mg
3) [Si
4O
10] [OH]
2NH
2O is because it has special nature.As: swelling, cohesiveness, adsorptivity, catalytic, thixotropy, suspension and cationic exchange or the like, so be widely used in each industrial circle.Wilkinite is to be the nonmetallic minerals of essential mineral composition with the montmorillonite, and structure is two 2:1 type crystal structure that silicon-oxy tetrahedron folder layer of aluminum oxygen octahedra is formed.Because there is some positively charged ion in the laminate structure that the montmorillonite structure cell forms, as Cu, Mg, Na, K etc., and the effect of these positively charged ions and montmorillonite structure cell is very insecure, easily by other cationic exchange, so have ion exchangeable preferably.
Use physico-chemical process and flocculation agent to dispose of sewage simultaneously, under its synergy, COD of sewage
CrAnd colourity can greatly be improved.
The present invention makes little electrolysis treatment and physico-chemical process be applied to vitamins B from more perfect pretreatment technology
12The treatment process of waste water.This novel little electrolysis of application, physico-chemical process treatment process can be avoided discharge of wastewater not up to standard, and invest little, instant effect, realize the recycle and the Sustainable development of water resources.
Summary of the invention
In order to address the above problem, the purpose of this invention is to provide a kind of little electrolysis pretreatment of utilizing, after entering the physico-chemical process processing again, enter the routine biochemistry treatment system and carry out biochemical treatment, water quality can reach little electrolysis, the physico-chemical process coupling of the method for emission standard and handle vitamins B
12Refine waste water plant and technology.
Technical scheme of the present invention is: vitamins B is handled in a kind of little electrolysis and physico-chemical process coupling
12Refine waste water plant, this device is made of raw water box 1, little electrolysis working shaft 2, little electrolyzer 3, mixing pond 4 wilkinite chemicals dosing plants 5, wilkinite preparing device 7, flocculation water tank 8, coagulating agent chemicals dosing plant 9, centrifugal conveying pump 10 and centrifugal separation equipment 11;
Wherein, described raw water box 1 connects by the upper pipes of little electrolysis working shaft 2 with little electrolyzer 3, and the pipeline that passes through of little electrolyzer 3 connects with the upper pipes of mixing pond 4; Wilkinite preparing device 7 connects by pipeline and wilkinite chemicals dosing plant 5 pipes, wilkinite chemicals dosing plant 5 is by pipeline and the upper end UNICOM of mixing pond 4, mix pond 4 by the upper end UNICOM of pipeline with flocculation water tank 8, coagulating agent chemicals dosing plant 9 is by the upper end UNICOM of pipeline with flocculation water tank 8, and the lower end of flocculation water tank 8 is by centrifugal conveying pump 10 and centrifugal separation equipment 11 UNICOMs.
Further, this device also comprises the NaOH chemicals dosing plant, and described NaOH chemicals dosing plant is by pipeline and the described upper end UNICOM of mixing pond 4.
Another object of the present invention provides above-mentioned little electrolysis and vitamins B is handled in the physico-chemical process coupling
12Refine the technology of waste water plant, may further comprise the steps:
1. little electrolysis treatment:
With vitamins B
12Refining waste water is former water, the former water that is stored in raw water box is entered little electrolyzer top by little electrolysis working shaft enter, and by whole cylinder, water outlet enters and mixes the pond with the flow velocity of 10～20m/hr; Remove certain C OD and colourity in the water, and wastewater pH is adjusted to 5～6; Wherein, the iron carbon volume ratio in little electrolyzer is 1: 2,1: 1 or 2: 1;
2. physico-chemical process is handled:
With natural sodium bentonite, quaternary cationics and water, join in the wilkinite preparing device according to 10: 3: 125 ratios, it is mixed post-heating to 90 ℃ lasting 1hr, promptly make modified alta-mud, in described mixing pond, add described modified alta-mud by the wilkinite chemicals dosing plant, mix 30min～2hr, gravity flow enters the flocculation water tank behind stop 30min～2hr, adds coagulating agent by the coagulating agent medicine system to the flocculation water tank; After mixing stirring 30min～1hr, by centrifugal conveying pump centrifugal separation equipment is sent in water outlet and carried out solid-liquid separation, produce the water that meets emission request after treatment;
Wherein, to go into amount be 6g/L～12g/L to described modified alta-mud; Described coagulating agent add-on is 1.5g/L～6g/L.
Further, when amount of inlet water or water quality produced fluctuation, if little electrolytic system fails waste water ph is adjusted between 5～6, then opening the NaOH medicine system, to add concentration in waste water be 10% NaOH solution, to guarantee wastewater pH 〉=5 in the described step 2.
Further, when amount of inlet water or water quality produced fluctuation, if little electrolytic system fails waste water ph is adjusted between 5～6, then opening the NaOH medicine system, to add concentration in waste water be 10% NaOH solution, to guarantee wastewater pH 〉=5 in the described step 2.
The invention has the beneficial effects as follows: owing to adopt technique scheme, the present invention adopts the relative conventional pretreatment vitamins B of little electrolysis-physico-chemical process system
12Waster water process is compared, and has following advantage:
(1) improved the biodegradability of waste water greatly.
(2) regulated wastewater pH, made it be more suitable for carrying out biochemical treatment.
(3) use little electrolysis as front-end processing, when improving treatment effect, reduced the cost of regulating pH.
(4) behind the engineering one-time investment, the more conventional dosing of working cost is handled much lower.
(5) greatly reduce the colourity of waste water.
(6) the back segment biochemical processing device is played protection and buffering effect, reduce pollutant load.
Description of drawings
Fig. 1 is that the little electrolysis of the present invention-physico-chemical process is handled vitamins B
12Refine the structural representation of waste water plant.
Fig. 2 is that the little electrolysis of the present invention-physico-chemical process is handled vitamins B
12Refine the method schematic diagram of waste water.
Among the figure:
1. raw water box 7. wilkinite preparing devices
2. little electrolysis working shaft 8. flocculation water tanks
3. little electrolyzer 9. coagulating agent chemicals dosing plants
4. mix pond 10. centrifugal conveying pumps
5. wilkinite chemicals dosing plant 11. centrifugal separation equipments
6.NaOH chemicals dosing plant
Embodiment
Fig. 1 is that the little electrolysis of the present invention-physico-chemical process is handled vitamins B
12Refine the structural representation of the device of waste water.As shown in Figure 1, little electrolysis-physico-chemical process is handled vitamins B
12This device of device that refines waste water is made of raw water box 1, little electrolysis working shaft 2, little electrolyzer 3, mixing pond 4 wilkinite chemicals dosing plants 5, NaOH chemicals dosing plant 6, wilkinite preparing device 7, flocculation water tank 8, coagulating agent chemicals dosing plant 9, centrifugal conveying pump 10 and centrifugal separation equipment 11;
Wherein, raw water box 1 connects by the upper pipes of little electrolysis working shaft 2 with little electrolyzer 3, and the lower end of little electrolyzer 3 connects with the upper pipes of mixing pond 4 by pipeline; Wilkinite preparing device 7 connects by pipeline and wilkinite chemicals dosing plant 5 pipes, wilkinite chemicals dosing plant 5 is by pipeline and the upper end UNICOM of mixing pond 4, NaOH chemicals dosing plant 6 is by the upper end UNICOM in pipeline mixing pond 4, the lower end of mixing pond 4 is by the upper end UNICOM of pipeline with flocculation water tank 8, coagulating agent chemicals dosing plant 9 is by the upper end UNICOM of pipeline with flocculation water tank 8, and the lower end of flocculation water tank 8 is by centrifugal conveying pump 10 and centrifugal separation equipment 11 UNICOMs.
Be stored in waste water in the raw water box 1 by the little electrolyzer 3 of entering of little electrolysis working shaft 2 with the flow velocity of 10～20m/hr by whole cylinder, remove COD and colourity in the water, and enter in the mixing pond 4 after pH value is adjusted to 5～6; The modified alta-mud of wilkinite preparing device 7 preparations adds mixing tank 4 by wilkinite medicine system 5, stir 30min～2hr, and stop 30min～2hr and promote wilkinite and waste water hybrid reaction, gravity flow enters flocculation water tank 8 then, coagulating agent adds in the flocculation water tank 8 by coagulating agent medicine system 9, after mixing stirring 30min～1hr, by centrifugal conveying pump centrifugal separation equipment is sent in water outlet and carried out solid-liquid separation, produce the water that meets emission request after treatment.Do not reach 5-6 if enter the pH value of mixing waste water in the pond 4, the pH value that adds NaOH adjusting waste water by NaOH medicine system 6 in mixing pond 4 reaches 5-6.
Embodiment 1:
1. little electrolysis treatment: with vitamins B
12Refining waste water is former water, the former water that is stored in raw water box is entered little electrolyzer top by little electrolysis working shaft enter, and by whole cylinder, removes COD and colourity in the water with the flow velocity of 10m/hr, and enters after wastewater pH is adjusted to 5 and mix the pond; Wherein, the iron carbon volume ratio in little electrolyzer is 1: 2.
2. physico-chemical process is handled:
Adding the wilkinite wilkinite by medicine system in described mixing pond, to add dose be 6g/L, mixes 30min, stop 1hr after gravity flow enter the flocculation water tank, add coagulating agent by the PAC medicine system to the flocculation water tank, the PAC consumption is 1.5g/L; After mixing stirring 30min, by centrifugal conveying pump centrifugal separation equipment is sent in water outlet and carried out solid-liquid separation, produce the water that meets emission request after treatment, the CODCr clearance in the water can reach 40%, and chroma removal rate reaches 80.5%.
Embodiment 2:
1. little electrolysis treatment: COD is that 6000mg/l and the waste water that contains a large amount of colour developing groups are former water, the former water that is stored in raw water box is entered little electrolyzer top by little electrolysis working shaft to be entered, flow velocity with 12m/hr passes through whole cylinder, remove COD and colourity in the water, and enter after wastewater pH is adjusted to 5 and mix the pond; Wherein, the iron carbon volume ratio in little electrolyzer is 1: 2.
2. physico-chemical process is handled:
Adding the wilkinite wilkinite by medicine system in described mixing pond, to add dose be 7.5g/L, mixes 1.5hr, stop 30min after gravity flow enter the flocculation water tank, add coagulating agent by the PAC medicine system to the flocculation water tank, the PAC consumption is 2.5g/L; After mixing stirring 40min, by centrifugal conveying pump centrifugal separation equipment is sent in water outlet and carried out solid-liquid separation, produce the water that meets emission request after treatment.COD
CrClearance can reach 55.4%, and chroma removal rate can reach 86.3%.
Embodiment 3:
1. little electrolysis treatment: COD is that 6000mg/l and the waste water that contains a large amount of colour developing groups are former water, the former water that is stored in raw water box is entered little electrolyzer top by little electrolysis working shaft to be entered, flow velocity with 18m/hr passes through whole cylinder, remove COD and colourity in the water, and enter after wastewater pH is adjusted to 5 and mix the pond; Wherein, the iron carbon volume ratio in little electrolyzer is 1: 2.
2. physico-chemical process is handled:
Adding the wilkinite wilkinite by medicine system in described mixing pond, to add dose be 7.5g/L, mixes 1.5hr, stop 50min after gravity flow enter the flocculation water tank, add coagulating agent by the PAC medicine system to the flocculation water tank, the PAC consumption is 4g/L; After mixing stirring 50min, centrifugal branch is sent in water outlet by centrifugal conveying pump.Produce the water that meets emission request, COD in the water through after treatment
CrClearance can reach 43%, and chroma removal rate reaches 83.24%.
Embodiment 4:
Waste water enters little electrolysis-physico-chemical process combined apparatus, and little electrolyzer is as the preposition pretreatment unit of materialization equipment, and waste water enters apparatus for physical Chemical treating with the speed of 20m/hr through little electrolyzer and by dosing pump wilkinite added and mix the pond.It is 12g/L that wilkinite adds dose.Waste water in mixing the pond with wilkinite thorough mixing 1.5hr, and enter the flocculation water tank through gravity flow after stopping 2hr.By the coagulation dosing pump coagulating agent is added the flocculation water tank.The coagulation consumption is 6g/L.Waste water again through after mixing stirring 1hr, is sent water outlet into centrifugal separation equipment with centrifugal conveying pump and is carried out solid-liquid separation in the flocculation water tank, produces the water that meets emission request after treatment.COD
CrClearance can reach 51.3%, and chroma removal rate reaches 82.16%.
Claims (4)
1. vitamins B is handled in little electrolysis and physico-chemical process coupling
12Refine waste water plant, it is characterized in that this device is made of raw water box (1), little electrolysis working shaft (2), little electrolyzer (3), mixing pond (4), wilkinite chemicals dosing plant (5), wilkinite preparing device (7), flocculation water tank (8), coagulating agent chemicals dosing plant (9), centrifugal conveying pump (10) and centrifugal separation equipment (11);
Wherein, described raw water box (1) connects by the upper pipes of described little electrolysis working shaft (2) with described little electrolyzer (3), and the pipeline that passes through of described little electrolyzer (3) connects with the upper pipes of mixing pond (4); Described wilkinite preparing device (7) connects by pipeline and described wilkinite chemicals dosing plant (5) pipe, described wilkinite chemicals dosing plant (5) is by pipeline and the upper end UNICOM of mixing pond (4), described mixing pond (4) is by the upper end UNICOM of pipeline with flocculation water tank (8), described coagulating agent chemicals dosing plant (9) is by the upper end UNICOM of pipeline with flocculation water tank (8), and described flocculation water tank (8) is by described centrifugal conveying pump (10) and described centrifugal separation equipment (11) UNICOM.
2. vitamins B is handled in little electrolysis according to claim 1 and physico-chemical process coupling
12Refine waste water plant, it is characterized in that this device also comprises NaOH chemicals dosing plant (6), described NaOH chemicals dosing plant (6) is used for adding NaOH solution to mixing pond (4) by pipeline and the described upper end UNICOM of mixing pond (4), regulates the pH value of waste water.
3. vitamins B is handled in little electrolysis according to claim 1 and 2 and physico-chemical process coupling
12Refine the technology of waste water plant, it is characterized in that, may further comprise the steps:
1. little electrolysis treatment:
With vitamins B
12Refining waste water is former water, the former water that is stored in raw water box is entered little electrolyzer top by little electrolysis working shaft enter, and by whole cylinder, water outlet enters and mixes the pond with the flow velocity of 10～20m/hr; Remove certain C OD and colourity in the water, and wastewater pH is adjusted to 5～6; Wherein, the iron carbon volume ratio in little electrolyzer is 1: 2,1: 1 or 2: 1.
2. physico-chemical process is handled:
With natural sodium bentonite, quaternary cationics and water, join in the wilkinite preparing device according to 10: 3: 125 ratios, it is mixed post-heating to 90 ℃ lasting 1hr, promptly make modified alta-mud, in described mixing pond, add described modified alta-mud by the wilkinite chemicals dosing plant, mix 30min～2hr, gravity flow enters the flocculation water tank behind stop 30min～2hr, adds coagulating agent by the coagulating agent medicine system to the flocculation water tank; After mixing stirring 30min～1hr, by centrifugal conveying pump centrifugal separation equipment is sent in water outlet and carried out solid-liquid separation, produce the water that meets emission request after treatment;
Wherein, to go into amount be 6g/L～12g/L to described modified alta-mud; Described coagulating agent add-on is 1.5g/L～6g/L.
4. vitamins B is handled in little electrolysis according to claim 3 and physico-chemical process coupling
12Refine the technology of waste water plant, it is characterized in that, when amount of inlet water or water quality generation fluctuation, fail waste water ph is adjusted between 5～6 in the described step 2 as if little electrolytic system, then opening the NaOH medicine system, to add concentration in waste water be 10% NaOH solution, to guarantee wastewater pH 〉=5.
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|---|---|---|---|
| CN 201010513042 CN101973659A (en) | 2010-10-12 | 2010-10-12 | Device and method for refining waste water by treating vitamin B12 by means of co-use of micro-electrolysis and physicochemical method |
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|---|---|---|---|
| CN 201010513042 CN101973659A (en) | 2010-10-12 | 2010-10-12 | Device and method for refining waste water by treating vitamin B12 by means of co-use of micro-electrolysis and physicochemical method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295371A (en) * | 2011-08-23 | 2011-12-28 | 同济大学 | Integrated-processing process for river bottom-mud dredging residual water and equipment thereof |
| CN102329048A (en) * | 2011-08-11 | 2012-01-25 | 湖北惠生药业有限公司 | Method for treating wastewater produced during chemical synthesis of vitamin B6 |
| CN102381787A (en) * | 2011-05-31 | 2012-03-21 | 南京大学 | Decoloration method for fermentation wastewater biochemical treatment tail water |
| CN102826721A (en) * | 2012-09-20 | 2012-12-19 | 艾特克控股集团有限公司 | Method for treating wastewater being generated during vitamin C production |
| CN110921924A (en) * | 2019-12-25 | 2020-03-27 | 南通市常海食品添加剂有限公司 | Environment-friendly treatment method of folic acid wastewater |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381787A (en) * | 2011-05-31 | 2012-03-21 | 南京大学 | Decoloration method for fermentation wastewater biochemical treatment tail water |
| CN102381787B (en) * | 2011-05-31 | 2013-04-10 | 南京大学 | Decoloration method for fermentation wastewater biochemical treatment tail water |
| CN102329048A (en) * | 2011-08-11 | 2012-01-25 | 湖北惠生药业有限公司 | Method for treating wastewater produced during chemical synthesis of vitamin B6 |
| CN102329048B (en) * | 2011-08-11 | 2012-10-03 | 湖北惠生药业有限公司 | Method for treating wastewater produced during chemical synthesis of vitamin B6 |
| CN102295371A (en) * | 2011-08-23 | 2011-12-28 | 同济大学 | Integrated-processing process for river bottom-mud dredging residual water and equipment thereof |
| CN102826721A (en) * | 2012-09-20 | 2012-12-19 | 艾特克控股集团有限公司 | Method for treating wastewater being generated during vitamin C production |
| CN110921924A (en) * | 2019-12-25 | 2020-03-27 | 南通市常海食品添加剂有限公司 | Environment-friendly treatment method of folic acid wastewater |
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Application publication date: 20110216 |