CN105384316A - Electronic industrial fluoride, ammonia and nitrogen-containing wastewater treatment method - Google Patents
Electronic industrial fluoride, ammonia and nitrogen-containing wastewater treatment method Download PDFInfo
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/346—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers
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Abstract
The present invention relates to an electronic industrial fluorine, ammonia and nitrogen-containing wastewater treatment method, which is as follows: (1), processing wastewater according to ammonia and nitrogen removal step, fluorine removal step and filtering step in turn; and (2), passing the wastewater treated by the step (1) in turn through an ultrafiltration membrane device, a cartridge filter and a reverse osmosis membrane device for processing to obtain regenerated recycle-water and concentrated water, wherein before the wastewater enters the ultrafiltration membrane device, a bactericide is added into the wastewater, after the wastewater passes through the cartridge filter and before the wastewater enters the reverse osmosis membrane device, a reducing agent is added into the wastewater to remove the bactericide in the wastewater. According to the method, addition of the reducing agent after the cartridge filter is put forward for the first time, on the one hand, no hazard is caused to the reverse osmosis membrane device, on the other hand the cartridge simplify operation and reduce cost.
Description
Technical field
The invention belongs to technical field of waste water processing, particularly the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry.
Background technology
Along with the development of electronic industrial technology particularly integrated circuit (IC) chip industrial technology, the electronic industry waste water particularly fluorine-containing nitrogen-containing wastewater of electronic industry is treated as the outstanding difficult problem in water treatment field.Electronic industry employs chemical agents as a large amount of in hydrofluoric acid, sulfuric acid, phosphoric acid, ammoniacal liquor, hydrochloric acid, organic solvent etc. usually in procedure for producing, make the waste water discharged contain a large amount of compositions surrounding enviroment being had to pollution, what exacerbate China's water pollutions and shortage of water resources situation sternly completes degree.
It is large that the fluorine-containing nitrogen-containing wastewater of electronic industry has the water yield, and pollutant component is complicated, and contaminative is strong, and biodegradability is poor, total dissolved solidss salt (TDS), ammonia nitrogen and content of fluoride high.Electronic enterprise (integrated circuit (IC) chip enterprise) does not have ripe effective treatment process to such waste water at present, generally after simply except fluorine process, can only enter municipal sewage plant and focus on.Due to such wastewater biodegradability difference (BOD/COD < 0.1), and due to the limitation of municipal sewage plant's Technology, in water outlet, total nitrogen is often not up to standard, easily cause the eutrophication of discharging water body, particularly effectively can not remove some specific pollutants (such as fluorine) and concentration can only be reduced by dilution.Face the ecotope be on the rise, national requirements industrial enterprise must implement the principles and policies of " energy-saving and emission-reduction ", in the environmental impact assessment of industrial enterprise use water rich and influential family is given an written reply except requiring discharged wastewater met the national standard, also the reclamation rate that waste water must reach certain is explicitly called for, conventional treatment process the more impossible realization of discharge of decreasing pollution thing effectively can not effectively reduce the quantity discharged of waste water by wastewater regenerating and recycling, realize recycling economy.Therefore, treatment process must be improved in wastewater treatment process, to greatest extent the quantity discharged of decreasing pollution thing, alleviate the pollution to surrounding enviroment, improve the regeneration rate of waste water simultaneously, save valuable water resources.
Two membrane technique be ultrafiltration/micro-filtration (UF/MF) technology is combined with reverse osmosis (RO) technology together with technique, this technique has been widely used in pure water and the ultrapure water preparation in the fields such as chemical industry, electric power, electronics, pharmacy, petrochemical industry, weaving, food at present, has and also apply in sewage recycling regeneration.Such as Chinese utility model CN201309866Y discloses a kind of waste water recycling treatment unit adopting " video disc filtration-ultra-filtration membrane device-intermediate water tank-security personnel's filtration-reverse osmosis " technique.
Though existing existing process and the reuse adopting the method and apparatus of ultrafiltration and reverse osmosis combination to carry out sewage, but the situation of the operation from existing electronic industry wastewater treatment film device, mainly there are the following problems:
1. the cartridge filter arranged between ultra-filtration membrane device and reverse osmosis unit frequently blocks, and needs often to change, and brings inconvenience, increase cost for wastewater treatment simultaneously to production;
2. the cleaning performance of reverse osmosis membrane apparatus is bad, and the work-ing life of reverse osmosis membrane is shorter.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, provides a kind for the treatment of process can effectively avoiding cartridge filter that the fluorine-containing nitrogen-containing wastewater of electronic industry of blocking occurs.
For solving above technical problem, the present invention takes following technical scheme:
A treatment process for the fluorine-containing nitrogen-containing wastewater of electronic industry, in the fluorine-containing nitrogen-containing wastewater of electronic industry, content of fluoride ion is for being not less than 20mg/L, and ammonia-nitrogen content is for being not less than 15mg/L, and wastewater pH is 6 ~ 9, and described method comprises the steps:
(1), by waste water according to except ammonia nitrogen operation → process except the flow process of fluorine operation → filter progress, described ammonia nitrogen operation of removing adopts chemical denitrogenation, described fluorine operation of removing takes chemical reaction precipitation to be separated the mode combined with coagulating sedimentation, and described filter progress is filtered by quartz sand filter tank by waste water;
(2), make the waste water through step (1) carry out process through ultra-filtration membrane device, cartridge filter and reverse osmosis membrane apparatus successively and obtain regenerated recycle-water and dense water, wherein, after quartz sand filter, in the forward direction waste water that enters ultra-filtration membrane device, add sterilant at waste water, at waste water after cartridge filter, add reductive agent in the forward direction waste water that enters reverse osmosis membrane apparatus with by the sterilant reaction removing in waste water.
Further, in step (2), described sterilant is NaClO, and described reductive agent is NaHSO
3.
Preferably, described sterilant add the 3*10 that weight is described waste water weight
-6~ 8*10
-5doubly, the molar ratio of described reductive agent and described sterilant is 1.5 ~ 2:1, feeding intake by PLC control, according to process flow automatic feeding of described sterilant.The benefit done like this to kill the bacterium of the included collection of cartridge filter in cartridge surface timely and effectively, effectively prevent the breeding of bacterium from forming raw fouling to filter core, at utmost extend the work-ing life of filter core, so not only effectively reduce the running cost of consumptive material, the more important thing is working time and the efficiency of effective raising equipment.
According to a concrete and preferred aspect of the present invention, the first intermediate pool was established before ultra-filtration membrane device, the first high-pressure pump is established between the first intermediate pool and ultra-filtration membrane device, the first pipeline is used to be communicated with ultra-filtration membrane device with described first intermediate pool respectively with water outlet by the water-in of the first high-pressure pump with second pipe respectively, waste water after step (1) process is passed in the first intermediate pool, described sterilant is added from described second pipe.
According to another concrete and preferred aspect of the present invention, the second intermediate pool is established between ultra-filtration membrane device and cartridge filter, the second high-pressure pump is established between the second intermediate pool and cartridge filter, use the 3rd pipeline the second intermediate pool to be communicated with ultra-filtration membrane device, use the 4th pipeline to be communicated with cartridge filter with described second intermediate pool respectively with water outlet by the water-in of the second high-pressure pump with the 5th pipeline respectively.
According to an also preferred aspect of the present invention, third high press pump is established between cartridge filter and reverse osmosis membrane apparatus, use the 6th pipeline to be communicated with reverse osmosis membrane apparatus with cartridge filter respectively with water outlet by the water-in of third high press pump with the 7th pipeline respectively, reductive agent is added by the 6th pipeline.
Further, the ratio that described regenerated recycle-water accounts for described waste water is 68% ~ 78%, is generally about about 70%.
Further, in waste water, to pass into oxidizer containing chlorine the ammonia nitrogen in waste water and oxidizer containing chlorine are reacted be converted into nitrogen and remove except ammonia nitrogen operation is specially described in step (1), described oxidizer containing chlorine is the Cl of liquid state or gaseous state
2;
Except chemical reaction precipitation in fluorine operation points to the material that adds calcium ions in waste water and make the fluorion in waste water react under the condition of pH6 ~ 7 to be converted into Calcium Fluoride (Fluorspan) described in step (1), the material of described calcium ions is one or more the combination be selected from calcium oxide, calcium hydroxide or soluble calcium salt, it is instigate the de-steady flco that formed of the Calcium Fluoride (Fluorspan) of generation chemistry under the effect of coagulating agent to strengthen sedimentation effect that described coagulating sedimentation is separated, then is separated with water by precipitation;
Preferably, described reverse osmosis membrane apparatus comprises the first reverse osmosis membrane unit of multiple parallel connection and the second reverse osmosis units of multiple parallel connection, waste water after cartridge filter filters is divided into multichannel, enter described multiple first reverse osmosis units to be respectively separated, the water outlet of described multiple first reverse osmosis units is as regenerated recycle-water, the dense moisture of described multiple first reverse osmosis units becomes multichannel to enter described multiple second reverse osmosis units to be separated, the water outlet of described multiple second reverse osmosis units is as regenerated recycle-water, the number of the second reverse osmosis units is less than the number of the first reverse osmosis units.Such as the first reverse osmosis units has 17, and the second reverse osmosis units is 9.
According to a preferred aspect of the present invention: except in ammonia nitrogen operation, 7.6 ~ 8.0mg/LCl is dropped into 1mg/L ammonia nitrogen in waste water
2ratio in waste water, add Cl
2, and points two batches add Cl
2, first batch of add-on is 65 ~ 75%, and remaining second batch adds, and is adding first batch of Cl
2afterwards, add and first batch of Cl added
2the alkali of equivalent with in and Cl
2react with ammonia nitrogen the hydrochloric acid produced, and then add second batch of Cl
2.In addition, the material that the ratio dropping into 2.3 ~ 2.5mg/L calcium ion with 1mg/L fluorion in waste water adds calcium ions in reaction tank is preferred.
Preferably, the different and different, specific as follows of the ratio of fluorinion in waste water and ammonia-nitrogen content are looked except ammonia nitrogen operation with except the concrete embodiment of fluorine operation:
When in the fluorine-containing nitrogen-containing wastewater of electronic industry, ammonia-nitrogen content is less than 1:2.5 with the ratio of content of fluoride ion, in ammonia nitrogen operation, the described alkali added is calcium hydroxide, except in fluorine operation, calcium oxide is added to regulate pH between 6 ~ 7 in the waste water after completing except ammonia nitrogen operation, and then add soluble calcium salt, afterwards, coagulating agent is added under the state stirred, wherein, except the calcium hydroxide added in ammonia nitrogen operation, total input amount except the calcium hydroxide added in fluorine operation and soluble calcium salt meets 1mg/L fluorion in waste water and drops into the proportion requirement of 2.3 ~ 2.5mg/L calcium ion, above-mentioned steps is all carried out in a reaction tank, afterwards, make the water outlet of reaction tank gravity flow enter settling pond precipitation and within 1 ~ 2 hour, obtain fluorinion concentration not higher than upper strata supernatant liquor and the mud of 9mg/L.
When in the fluorine-containing nitrogen-containing wastewater of electronic industry, ammonia-nitrogen content is 1:1.75 ~ 2.5 with the ratio of content of fluoride ion, in ammonia nitrogen operation, the described alkali added is calcium hydroxide, except in fluorine operation: again add calcium hydroxide to completing steps except in the waste water after ammonia nitrogen operation, the calcium hydroxide that this time adds meets 1mg/L fluorion in waste water with total input amount of the calcium hydroxide added in ammonia nitrogen operation and drops into the proportion requirement of 2.3 ~ 2.5mg/L calcium ion, simultaneously, adding sodium hydroxide regulates wastewater pH to be 6 ~ 7, and coagulating agent is added under whipped state, above-mentioned steps is all carried out in a reaction tank, afterwards, make the water outlet of reaction tank gravity flow enter settling pond precipitation and within 1 ~ 2 hour, obtain fluorinion concentration not higher than upper strata supernatant liquor and the mud of 9mg/L.
When in the fluorine-containing nitrogen-containing wastewater of electronic industry, ammonia-nitrogen content is greater than 1:1.75 with the ratio of content of fluoride ion, the material of the calcium ions added is chosen as calcium hydroxide, in ammonia nitrogen operation, drop into all except the calcium hydroxide needed for fluorine as in and the alkali of hydrochloric acid of ammonia nitrogen reaction generation, the alkali sodium hydroxide of deficiency is supplied; Except in fluorine operation, sodium hydroxide is added to regulate wastewater pH for 6 ~ 7 in the waste water after completing except ammonia nitrogen operation, and coagulating agent is added under the state stirred, above-mentioned steps is all carried out in a reaction tank, afterwards, make the water outlet of reaction tank gravity flow enter settling pond precipitation and within 1 ~ 2 hour, obtain fluorinion concentration not higher than upper strata supernatant liquor and the mud of 9mg/L.
Above-mentioned coagulating agent can for being selected from the combination of one or more in various coagulating agent such as polymerize aluminum chloride (PAC), the polyacrylamide (PAM) etc. of technical field of waste water processing routine.
According to the different of the ratio of fluorinion in waste water and ammonia-nitrogen content and the above-mentioned different embodiment selected, deficiency that the material due to calcium ions adds can be solved and the problem of cause the material of the not high problem of fluorine removing rate and calcium ions to add calcium ion content in excessive water outlet is too high equipment easy fouling when causing subsequent disposal, guarantee that effluent quality reaches subsequent treatment process requirement.
Preferably, on suction culvert He in reaction tank, install ammonia nitrogen on-line monitoring instrument apparatus, the ammonia-nitrogen content in Real-Time Monitoring waste water, monitoring result feeds back to Controlling System and in reaction tank, adds Cl in proportion to control chlorinating machine
2, so, can solve because the not high problem of chlorination deficiency removal ammonia nitrogen efficiency and chlorination add the too high problem of excessive chlorine residue, guarantee that effluent quality reaches subsequent disposal procedure calls.Further preferably, in reaction tank, also install fluorion on-line computing model and online pH meter, the pH value of Real-Time Monitoring fluorinion in waste water content and waste water, monitoring result feeds back to Controlling System, Controlling System, according to fluorinion in waste water content, adds the material of calcium ions in waste water.
The present invention adopts the ammonia nitrogen in chemical chlorination denitrogenation removal waste water, effectively reduces ammonia-nitrogen content, fast, efficiently, stablizes; When the ammonia nitrogen concentration variation range of intaking is larger, only need change chlorine dosage according to reaction ratio just can reach treatment effect, and the trade effluent of the method energy flexible adaptation ammonia nitrogen concentration strong variations therefore adopted, namely the impact resistance of the method is stronger.And adopt the bioremediation of conventional removal ammonia nitrogen to need cultivation bacterial classification, initial failure period long, and the volume of biological reaction tank has been fixed, and cannot reach gratifying removal effect when ammonia nitrogen concentration strong variations.
The present invention adopts and first carries out chlorination except ammonia nitrogen, rear interpolation can form the material (such as calcium oxide/lime of water-fast Calcium Fluoride (Fluorspan) with fluorion, calcium hydroxide, the calcium salts such as calcium chloride), not only treatment effect is stable good, and utilizes the alkali produced except the material needing in fluorine process to add to neutralize the acid of denitrogenating and producing in reaction, is conducive to the control of water outlet pH value, reach best defluorination effect, and simple to operate
In filter progress, waste water is preferably 5.5 ~ 7.5m by the filtering velocity in quartz sand filter tank
3/ m
2h, quartz sand filter tank is preferably V-type filter tank.
According to the present invention, when containing ring-type organonitrogen and/or larger molecular organics in waste water, step (1) carries out ozone and active carbon process to waste water after being also preferably included in filter progress, described ozone and activated carbon process comprises the ozone treatment step and charcoal absorption step of carrying out successively, wherein said ozonize is carried out in ozone contact tank, in ozone contact tank, ozone is supplied by ozonizer, ozone addition is 2.5 ~ 3.0mg/L waste water, and the treatment time is 20 ~ 40 minutes; Described charcoal absorption is carried out interior being filled with in the activated carbon filter of carbon leaching material.
After step (1), before step (2), also ozone and active carbon process is carried out to waste water, described ozone and activated carbon process comprises the ozone treatment step and charcoal absorption step of carrying out successively, wherein said ozonize is carried out in ozone contact tank, in ozone contact tank, ozone is supplied by ozonizer, ozone addition is 2.5 ~ 3.0mg/L waste water, and the treatment time is 20 ~ 40 minutes; Described charcoal absorption is carried out interior being filled with in the activated carbon filter of carbon leaching material.According to the practice of applicant, to the waste water containing ring-type organonitrogen and larger molecular organics, if do not carry out ozone and active carbon process just directly carry out Ultra filtration membrane, be then very easy to the problem occurring that film blocks, have impact on the process of waste water greatly.Therefore, this invention, for this kind of waste water, utilizes ozone that the ring-type organonitrogen in waste water and larger molecular organics are decomposed/be broken into small-molecule substance, and utilizes the small-molecule substance absorption removing that the gac with good adsorption properties will produce.
Preferably, described ultra-filtration membrane device employing membrane pore size is the ultrafiltration membrance filter element of 8 ~ 12nm, and in a specific embodiment, ultra-filtration membrane aperture is 10nm.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
Present inventor puts into practice favorite outer discovery in a large number at it, and in the process of the fluorine-containing nitrogen-containing wastewater of electronic industry, the blocking of cartridge filter effectively can be avoided, delays and be alleviated to the existence of sterilant.Before cartridge filter, adding reductive agent with tradition removes compared with the method for sterilant, the present invention proposes to add reductive agent first after cartridge filter, on the one hand, reductive agent is added in this stage, reductive agent still fully can react with the sterilant in waste water, thus harm can not be formed to reverse osmosis membrane apparatus, on the other hand, reductive agent is added in this stage, effectively avoid, delay and alleviate the blocking of cartridge filter, do not need often to change cartridge filter, contribute to improving processing efficiency, simplifying the operation and reduce costs.
Accompanying drawing explanation
The schematic diagram of the treatment unit that Fig. 1 adopts for uf processing of the present invention and reverse-osmosis treated;
Wherein: 1, ultra-filtration membrane device; 2, the first intermediate pool; 3, the first high-pressure pump; 4, cartridge filter; 5, the second intermediate pool; 6, the second high-pressure pump; 7, third high press pump; 8, reverse osmosis membrane apparatus; A, the first pipeline; B, second pipe; C, the 3rd pipeline; D, the 4th pipeline; E, the 5th pipeline; F, the 6th pipeline.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention will be further described in detail, but the invention is not restricted to following examples.
Following embodiment additive amount is numerical value during season in spring and autumn.
The fluorine-containing nitrogen-containing wastewater of certain electronic industry contains the pollutents such as a large amount of fluorine, ammonia nitrogen, organonitrogen, phosphorus and suspended solid, and in water, total dissolved solidss salts contg is higher.
Present invention process comprises makes waste water successively through overregulating, except ammonia nitrogen operation, except fluorine operation, filter progress, ozone and active carbon process, uf processing, reverse osmosis membrane processing, obtain regenerated recycle-water and dense water.
Concrete technology step is as follows:
(1), regulate: due to discharge water quality and water yield aspect all have certain malconformation, therefore equalizing tank carries out water quality and water yield equilibrium to waste water is set.
(2), except ammonia nitrogen operation, except the chemical reaction of fluorine operation precipitate, except the coagulating of fluorine operation: waste water through lift pump promote enter the reaction tank being provided with stirrer carry out chemistry except ammonia nitrogen operation, except the chemical reaction of fluorine operation precipitate, except the coagulating of fluorine operation, specific as follows:
1. according to the water quality characteristics of waste water, adopt: (1) installs ammonia nitrogen on-line monitoring instrument apparatus on suction culvert He in reaction tank, ammonia-nitrogen content in Real-Time Monitoring waste water, monitoring result feeds back to Controlling System to control the amount that chlorinating machine adds liquid chlorine in reaction tank, and points two batches add liquid chlorine (by first about 70%, second batch about 30% adds), be of value to the process control of removal of ammonia and nitrogen and improve the removal efficiency of ammonia nitrogen.Can solve because the not high problem of chlorination deficiency removal ammonia nitrogen efficiency and chlorination add the too high problem of excessive chlorine residue, guarantee that effluent quality reaches subsequent treatment process requirement.The addition of liquid chlorine generally needs the concentration ratio of 7.6 ~ 8.0mg/L liquid chlorine to add by 1mg/L ammonia nitrogen in waste water.
2. due in waste water, the ratio of ammonia nitrogen/content of fluoride ion is less than 1:2.5, then according to each reaction that following implementation Process is above-mentioned: first add first liquid chlorine removal unit and divide ammonia nitrogen, add the calcium hydroxide with liquid chlorine equivalent added by first batch again, on the one hand calcium hydroxide can in and the hydrochloric acid that produces except ammonia nitrogen of liquid chlorine, the calcium ion of calcium hydroxide can generate with the reaction of part fluorion the Calcium Fluoride (Fluorspan) being insoluble in water on the other hand, then add second batch time liquid chlorine and remove remaining ammonia nitrogen in waste water, again adding calcium hydroxide neutralization makes pH value control between 6.0 ~ 7.0, be beneficial to the formation of calcium fluoride crystal, not enough calcium ion part is supplemented by adding calcium chloride again, finally most fluorion can be converted into Calcium Fluoride (Fluorspan).
3. the waste water, after above-mentioned steps adds coagulating agent (PB1 gene, polyacrylamide PAM or the combination of the two) under whipped state.The Calcium Fluoride (Fluorspan) produced except fluorine reaction due to subordinate phase is insoluble fine particle, and precipitable property is poor, the fine particle chemistry comprising Calcium Fluoride (Fluorspan) can be made to take off steady and form more big flocculating body, reinforced deposition effect by dosing coagulant.
Adopt above-mentioned additive and coagulation-settlement process can remove phosphorus simultaneously, precipitated by settling pond after the phosphorus in waste water generates calcium phosphate granules with lime reaction in reaction tank and remove.
The water outlet gravity flow of reaction tank enters settling pond, precipitates after 1 ~ 2 hour, and most of fluorochemical, suspended substance and the partial organic substances precipitation in waste water forms mud discharging and removes.The mud of settling pond is transported to sludge dehydration device and sludge dewatering is become mud cake, and mud cake contains calcium component, can be exploited, and be the very good material manufacturing environmental protection fragment of brick, storage basin supernatant liquor and filtrate are back to equalizing tank circular treatment.Content of fluoride ion is not higher than 9mg/L after testing for upper strata supernatant liquor, and ammonia-nitrogen content, lower than 0.5mg/L, can make it flow automatically and enter V-type quartz sand filter.
(3), filter progress and the process of V-type quartz sand filter tank: the supernatant liquid gravity flow of settling pond is with the V-type filter tank of the quartz sand filter media layer of uniform grading, and filtering velocity controls at 5.5 ~ 7.5m
3/ m
2between h, mainly removed in settling pond by physical filtering effect and fail the fine suspension of sedimentation and gelatinoid.When filter tank is run filtering layer blocking after for some time and affected filtering velocity, available air-water backwashing filtering layer recovery filtering velocity, rinse water is back to equalizing tank circular treatment.Waste water after this step process can carry out regeneration by device for ultrafiltration membrane substantially.
(4), ozone contact tank process: the water outlet in quartz sand filter tank enters ozone contact tank, supply ozone to the ozonation aerated dish in pond by ozonizer, utilize the part cyclic organonitrogen and part larger molecular organics that contain in the Strong oxdiative ability Decomposition Wastewater of ozone.Ozone addition is 2.5 ~ 3.0mg/L, and oxidization time is generally 30 minutes.
(5), activated carbon filter process: the water outlet of ozone contact tank enters activated carbon filter, carbon leaching material is filled with in this filter tank, small molecules organonitrogen, Adsorption of Organic that the absorption property utilizing gac good will be generated by ozone oxidation, then carry out biological degradation by the small organic molecule of biology to absorption of attached work on activated carbon surface.When filter tank is run filtering layer blocking after for some time and affected filtering velocity, available air-water backwashing filtering layer recovery filtering velocity, rinse water is back to equalizing tank circular treatment.
Ozone and active carbon treatment process is the sfgd. to film separating system; the pollution of above-mentioned pollutent to follow-up reverse osmosis membrane can be reduced; reduce its cleaning and replacement frequency, extend the work-ing life of membrane element, reduce facility investment, working cost and the chlorine dosage etc. to follow-up disinfection of effluent process.
(6), uf processing: the present embodiment mainly selects ultrafiltration membrance filter element, the feature of more than 100,000 dalton is mainly for macromolecule organic molecular weight in waste water, on the satisfied basis removing turbidity, colloid, bacterium, virus etc., suitable membrane pore size also must be selected to ensure above-mentioned organic removal, and this ultrafiltration apparatus membrane pore size is about 10nm.This equipment can remove turbidity, colloid, bacterium, virus and most organic etc., ensures the water outlet after by ultrafiltration substantially not containing any suspended substance, keeps high quality for a long time.
(7), reverse-osmosis treated: in this example, reverse osmosis membrane apparatus comprises 17 the first reverse osmosis units in parallel and 9 the second reverse osmosis units in parallel.Waste water be divided into 17 tunnels enter respectively 17 first reverse osmosis units be separated after obtain regenerated recycle-water and dense water, dense moisture becomes 9 tunnels to enter 9 the second reverse osmosis units respectively, through second reverse osmosis units be separated after obtain regenerated recycle-water and dense water, concentrated water discharge.
See table 1, it is the present embodiment Inlet and outlet water water quality contrast table, comprise pollutant load main in water waste water, and GB5749-2006 " drinking water sanitary standard " leading indicator of national up-to-date promulgation, and reuse water water-quality guideline actual after the present embodiment process; By more known, the reuse water water quality carrying out processing through the present embodiment reaches even greatly be better than above-mentioned " drinking water sanitary standard " completely, and wherein the TDS concentration of reuse water is lower, completely can as the primary pure water of electronic industry enterprise production.
Table 1 is intake principal pollutant and effluent quality leading indicator contrast table
As shown in Figure 1, the schematic diagram of the treatment unit that uf processing and reverse-osmosis treated adopt is carried out after there is shown activated carbon filter process.See Fig. 1, the first intermediate pool 2 was established before ultra-filtration membrane device 1, between the first intermediate pool 2 and ultra-filtration membrane device 1, establish the first high-pressure pump 3, use the first pipeline a to be communicated with ultra-filtration membrane device 1 with the first intermediate pool 2 respectively with water outlet by the water-in of the first high-pressure pump 3 with second pipe b respectively.The second intermediate pool 5 is established between ultra-filtration membrane device 1 and cartridge filter 4, the second high-pressure pump 6 is established between the second intermediate pool 5 and cartridge filter 4, use the 3rd pipeline c the second intermediate pool 5 to be communicated with ultra-filtration membrane device 1, use the 4th pipeline d to be communicated with cartridge filter 4 with the second intermediate pool 5 respectively with water outlet by the water-in of the second high-pressure pump 6 with the 5th pipeline e respectively.Between cartridge filter 4 and reverse osmosis membrane apparatus 8, establish third high press pump 7, use the 6th pipeline f to be communicated with reverse osmosis membrane apparatus 8 with cartridge filter 4 respectively with water outlet by the water-in of third high press pump 7 with the 7th pipeline g respectively.
Carry out, in the process of wastewater treatment, in waste water, adding sterilant NaClO by second pipe b at employing said apparatus, in waste water, add reductive agent NaHSO by the 6th pipeline f
3.NaClO adds the about 5*10 that weight is waste water weight
-6doubly, NaHSO
3be 1.8:1 with the molar ratio of NaClO, sterilant NaClO and reductive agent NaHSO
3feed intake and all controlled by PLC, according to process flow automatic feeding.The sterilant NaClO added joins in waste water from second pipe b, in ultra-filtration membrane device 1, second intermediate pool 5, second high-pressure pump 6 and cartridge filter 4 this section of flow process, all effectively can kill the microorganisms such as the bacterium in waste water and suppress growing of microorganism, thus avoid microorganism to the pollution of ultra-filtration membrane, effectively prevent cartridge filter 4 from blocking simultaneously, improve the work-ing life of cartridge filter 4.The inventive method proves through long-time running, and cartridge filter is without the need to frequent replacing.Under continuous operation conditions, cartridge filter interval 30 ~ 40 days substantially, just needs to change, when water pollution is not especially severe, reuses after can cleaning.And traditional method cartridge filter 5 ~ 10 day time will be changed substantially, and cannot by cleaning after recycling.
Above to invention has been detailed description; its object is to allow the personage being familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence change that all spirit according to the present invention are done or modification, all should be encompassed in protection scope of the present invention.
Claims (10)
1. a treatment process for the fluorine-containing nitrogen-containing wastewater of electronic industry, described method comprises the steps:
(1), by described waste water according to except ammonia nitrogen operation → process except the flow process of fluorine operation → filter progress, described ammonia nitrogen operation of removing adopts chemical denitrogenation, described fluorine operation of removing takes chemical reaction precipitation to be separated the mode combined with coagulating sedimentation, and described filter progress is filtered by quartz sand filter tank by waste water;
(2), make the waste water through step (1) carry out process through ultra-filtration membrane device, cartridge filter and reverse osmosis membrane apparatus successively to obtain regenerated recycle-water and dense water, it is characterized in that:
After quartz sand filter, in the forward direction waste water that enters ultra-filtration membrane device, add sterilant at described waste water, and at waste water after cartridge filter, add reductive agent in the forward direction waste water that enters reverse osmosis membrane apparatus with by described sterilant reaction removing.
2. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 1, is characterized in that: in step (2), and described sterilant is NaClO, and described reductive agent is NaHSO
3.
3. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 1 and 2, is characterized in that: described sterilant add the 3*10 that weight is described waste water weight
-6~ 8*10
-5doubly, the molar ratio of described reductive agent and described sterilant is 1.5 ~ 2:1, feeding intake by PLC control, according to process flow automatic feeding of described sterilant.
4. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 1, it is characterized in that: before ultra-filtration membrane device, establish the first intermediate pool, the first high-pressure pump is established between the first intermediate pool and ultra-filtration membrane device, the first pipeline is used to be communicated with ultra-filtration membrane device with described first intermediate pool respectively with water outlet by the water-in of the first high-pressure pump with second pipe respectively, waste water after step (1) process is passed in the first intermediate pool, described sterilant is added from described second pipe.
5. the treatment process of the fluorine-containing nitrogen-containing wastewater of the electronic industry according to claim 1 or 4, it is characterized in that: between ultra-filtration membrane device and cartridge filter, establish the second intermediate pool, the second high-pressure pump is established between the second intermediate pool and cartridge filter, use the 3rd pipeline the second intermediate pool to be communicated with ultra-filtration membrane device, use the 4th pipeline to be communicated with cartridge filter with described second intermediate pool respectively with water outlet by the water-in of the second high-pressure pump with the 5th pipeline respectively.
6. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 5, it is characterized in that: between cartridge filter and reverse osmosis membrane apparatus, establish third high press pump, use the 6th pipeline to be communicated with reverse osmosis membrane apparatus with described cartridge filter respectively with water outlet by the water-in of third high press pump with the 7th pipeline respectively, described reductive agent is added by described 6th pipeline.
7. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 1, is characterized in that: the ratio that described regenerated recycle-water accounts for described waste water is 68% ~ 78%.
8. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 1, is characterized in that:
In waste water, to pass into oxidizer containing chlorine the ammonia nitrogen in waste water and oxidizer containing chlorine are reacted be converted into nitrogen and remove except ammonia nitrogen operation is specially described in step (1), described oxidizer containing chlorine is the Cl of liquid state or gaseous state
2;
Except chemical reaction precipitation in fluorine operation points to the material that adds calcium ions in waste water and make the fluorion in waste water react under the condition of pH6 ~ 7 to be converted into Calcium Fluoride (Fluorspan) described in step (1), the material of described calcium ions is one or more the combination be selected from calcium oxide, calcium hydroxide or soluble calcium salt, it is instigate the de-steady flco that formed of the Calcium Fluoride (Fluorspan) of generation chemistry under the effect of coagulating agent to strengthen sedimentation effect that described coagulating sedimentation is separated, then is separated with water by precipitation.
9. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 1, it is characterized in that: described step (1) carries out ozone and active carbon process to waste water after being also included in filter progress, described ozone and activated carbon process comprises the ozone treatment step and charcoal absorption step of carrying out successively, wherein said ozonize is carried out in ozone contact tank, in ozone contact tank, ozone is supplied by ozonizer, ozone addition is 2.5 ~ 3.0mg/L waste water, and the treatment time is 20 ~ 40 minutes; Described charcoal absorption is carried out interior being filled with in the activated carbon filter of carbon leaching material.
10. the method for the whole regeneration of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 1, it is characterized in that: described reverse osmosis membrane apparatus comprises the first reverse osmosis membrane unit of multiple parallel connection and the second reverse osmosis units of multiple parallel connection, waste water after cartridge filter filters is divided into multichannel, enter described multiple first reverse osmosis units to be respectively separated, the water outlet of described multiple first reverse osmosis units is as described regenerated recycle-water, the dense moisture of described multiple first reverse osmosis units becomes multichannel to enter described multiple second reverse osmosis units to be separated, the water outlet of described multiple second reverse osmosis units is as described regenerated recycle-water, the number of described second reverse osmosis units is less than the number of described first reverse osmosis units.
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