CN102126799B - Method for treating fluorine-containing and ammonia nitrogen-containing waste water in electronic industry - Google Patents
Method for treating fluorine-containing and ammonia nitrogen-containing waste water in electronic industry Download PDFInfo
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Abstract
The invention relates to a method for treating fluorine-containing and ammonia nitrogen-containing waste water in electronic industry. The method comprises an ammonia nitrogen removal procedure and a fluorine removal procedure, wherein the ammonia nitrogen removal procedure is as follows: Cl2 is added into waste water, wherein 7.6-8.0mg of Cl2 is added into every one liter of waste water containing 1mg of ammonia nitrogen, and the Cl2 is added in two batches; the addition amount for the first batch is 65-75%, and the addition amount for the second batch is the rest; after the first batch of Cl2 is added, alkali equivalent to the added Cl2 for the first batch is added to neutralize hydrochloric acid produced by the reaction of the Cl2 and ammonia nitrogen, and then, the second batch of Cl2 is added; and the fluorine removal procedure combines chemical reaction precipitation and coagulative precipitation separation. By firstly removing ammonia nitrogen and then removing fluorine, the invention achieves the advantages of stable and favorable treatment effect, high efficiency and high speed. The fluorine ion content and ammonia nitrogen content in the waste water treated by the invention are effectively reduced, and the waste water can be discharged or be subjected to further reclamation treatment to be reclaimed according to different environmental protection requirements.
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 particularly development of IC chip industrial technology of electronic industrial technology, the electronic industry waste water particularly fluorine-containing nitrogen-containing wastewater of electronic industry is treated as the outstanding difficult problem in the water treatment field.Electronic industry has been used in procedure for producing like a large amount of chemical agents such as hydrofluoric acid, sulfuric acid, phosphoric acid, ammoniacal liquor, hydrochloric acid, organic solvents usually; To make the waste water of discharging contain a large amount of have the composition of pollution to surrounding enviroment, aggravated that China's water pollutes and the shortage of water resources situation sternly complete degree.
It is big 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, characteristics such as total dissolved solidss salt (TDS), ammonia nitrogen and content of fluoride height.Electronic enterprise (IC chip enterprise) does not have the mature and effective treatment process to such waste water at present, after handling through simple defluorination, can only enter the municipal sewage plant and focus on generally speaking.Because such wastewater biodegradability poor (BOD/COD＜0.1); And because the limitation of municipal sewage plant's Technology; Total nitrogen is often not up to standard in the water outlet; Cause discharging the eutrophication of water body easily, particularly can not effectively remove and can only reduce concentration by dilution to some specific pollutants (such as fluorine).Face the ecotope that is on the rise; National requirements industrial enterprise must implement the principles and policies of " energy-saving and emission-reduction "; In to the water rich and influential family's of industrial enterprise environmental impact assessment reply except requiring discharged wastewater met the national standard; Also explicitly call for waste water must reach certain reclamation rate, the discharging that conventional treatment process can not reduce pollutent effectively more can not realize effectively reducing discharged waste water through wastewater regenerating and recycling, realizes recycling economy.Therefore, must in wastewater treatment process, improve treatment process, reduce the quantity discharged of pollutent to greatest extent, alleviate pollution, improve the regeneration rate of waste water simultaneously, the water resources of saves valuable surrounding enviroment.
Summary of the invention
Technical problem to be solved by this invention is in order to overcome the deficiency of prior art, the treatment process of the fluorine-containing nitrogen-containing wastewater of a kind of electronic industry to be provided, and it can remove fluorion and ammonia nitrogen in the waste water quickly and efficiently with lower cost.
For solving above technical problem, the present invention takes following technical scheme:
The treatment process of the fluorine-containing nitrogen-containing wastewater of a kind of electronic industry, content of fluoride ion is for being not less than 20mg/L in the fluorine-containing nitrogen-containing wastewater of said electronic industry, and ammonia-nitrogen content the treating method comprises following steps for being not less than 15mg/L:
(1), remove the ammonia nitrogen operation: in waste water, feeding oxidizer containing chlorine, to make ammonia nitrogen and oxidizer containing chlorine reaction conversion in the waste water be that nitrogen is removed, and said oxidizer containing chlorine is liquid state or gasiform Cl
2, and with 1mg/L ammonia nitrogen input 7.6～8.0mg/L Cl in the waste water
2Ratio in waste water, add Cl
2, wherein, divide two batches and add Cl
2, wherein first batch of add-on is 65～75%, remaining second batch of adding adding first batch of Cl
2Afterwards, add and first batch of Cl that is added
2The alkali of equivalent with in and Cl
2With the hydrochloric acid of ammonia nitrogen reaction generation, and then add second batch of Cl
2
(2), defluorination operation: take the chemical reaction deposition to separate the mode that combines with coagulating sedimentation; Wherein chemical reaction deposition is to point to that to add the material of calcium ions in the waste water and under the condition of pH 6～7, make the fluorion reaction conversion in the waste water be Calcium Fluoride (Fluorspan); The material of said calcium ions is one or more the combination that is selected from quicklime, calcium hydroxide or the soluble calcium salt; And the ratio that drops into 2.3～2.5mg/L calcium ion with 1mg/L fluorion in the waste water is added the material of calcium ions in reaction tank; It is to instigate Calcium Fluoride (Fluorspan) chemistry under the effect of coagulating agent of generation to take off steady formation flco to strengthen sedimentation effect, again through deposition and water sepn that said coagulating sedimentation separates.
Preferably, step (1) and the concrete embodiment of step (2) are looked ratio different and different, specific as follows of fluorion and ammonia-nitrogen content in the waste water:
When the ratio of ammonia-nitrogen content in the fluorine-containing nitrogen-containing wastewater of electronic industry and content of fluoride ion during less than 1: 2.5, in step (1), the said alkali of adding is calcium hydroxide; In the step (2); In completing steps (1) waste water afterwards, add calcium hydroxide regulating pH between 6～7, and then add soluble calcium salt, afterwards; Under the state that stirs, add coagulating agent; Wherein, total input amount of the calcium hydroxide that is added in the step (1), the calcium hydroxide that step (2) is added and soluble calcium salt satisfies the proportion requirement that the 1mg/L fluorion drops into 2.3～2.5mg/L calcium ion in the waste water, and above-mentioned steps is all carried out in a reaction tank; Afterwards, make the water outlet of reaction tank obtain upper strata supernatant and the precipitating sludge that fluorinion concentration is not higher than 9mg/L in 1～2 hour from flowing into the settling pond deposition.
When the ratio of ammonia-nitrogen content in the fluorine-containing nitrogen-containing wastewater of electronic industry and content of fluoride ion was 1: 1.75～2.5, in step (1), the said alkali of adding was calcium hydroxide; In the step (2): in completing steps (1) waste water afterwards, add calcium hydroxide once more; Total input amount of the calcium hydroxide that adds in the calcium hydroxide of this time adding and the step (1) satisfies the proportion requirement that the 1mg/L fluorion drops into 2.3～2.5mg/L calcium ion in the waste water; Simultaneously; Adding sodium hydroxide adjusting wastewater pH is 6～7, and under whipped state, adds coagulating agent, and above-mentioned steps is all carried out in a reaction tank; Afterwards, make the water outlet of reaction tank obtain upper strata supernatant and the precipitating sludge that fluorinion concentration is not higher than 9mg/L in 1～2 hour from flowing into the settling pond deposition.
When the ratio of ammonia-nitrogen content in the fluorine-containing nitrogen-containing wastewater of electronic industry and content of fluoride ion during greater than 1: 1.75; The material of the calcium ions that is added is chosen as calcium hydroxide; In step (1); Drop into the alkali of the hydrochloric acid that reaction produces with ammonia nitrogen in the required calcium hydroxide conduct of whole defluorinations, insufficient alkali is supplied with sodium hydroxide; In the step (2); In completing steps (1) waste water afterwards, adding sodium hydroxide, to regulate wastewater pH be 6～7; And at the state that stirs adding coagulating agent down; Above-mentioned steps is all carried out in a reaction tank, afterwards, makes the water outlet of reaction tank obtain upper strata supernatant and the mud that fluorinion concentration is not higher than 9mg/L in 1～2 hour from flowing into the settling pond deposition.
Above-mentioned coagulating agent can be for being selected from the for example combination of one or more in Poly aluminum Chloride (PAC) (PAC), the SEPIGEL 305 (PAM) etc. of the conventional various coagulating agent of technical field of waste water processing.
According to the different above-mentioned different embodiments selected of fluorion in the waste water with the ratio of ammonia-nitrogen content; Can solve the deficiency that adds owing to the material of calcium ions and cause the material of not high problem of fluorine removing rate and calcium ions to add the problem of equipment easy scale formation when calcium ion content is too high in the excessive water outlet causes subsequent disposal, guarantee that effluent quality reaches the subsequent treatment process requirement.
According to further embodiment of the present invention: said treatment process also comprises step (3): the upper strata supernatant in the settling pond is filtered from flowing into the silica sand filter tank; And step (4): the mud that deposition in the settling pond is produced is processed into available mud cake with dewatering unit.
Preferably, on suction culvert with in the reaction tank, ammonia nitrogen on-line monitoring instrument apparatus is installed, is monitored the ammonia-nitrogen content in the waste water in real time, monitoring result feeds back to system and in reaction tank, adds Cl in proportion with the control chlorinating machine
2, so, can solve because not enough not high problem and the chlorination of ammonia nitrogen efficient of removing of chlorination adds the too high problem of excessive chlorine residue, guarantee that effluent quality reaches the requirement of subsequent disposal operation.
Further preferably; Fluorion on-line monitoring appearance and online pH meter also are installed in reaction tank, are monitored the pH value of content of fluoride ion and waste water in the waste water in real time, monitoring result feeds back to system; System adds the material of calcium ions according to content of fluoride ion in the waste water in waste water.
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
1, the inventive method adopts chemical chlorination denitrogenation to remove the ammonia nitrogen in the waste water, has reduced ammonia-nitrogen content effectively, and is quick, efficient, stable; When the ammonia nitrogen concentration variation range of water inlet is big, only need to change chlorine dosage and just can reach treatment effect according to reaction ratio, the trade effluent of the method ability flexible adaptation ammonia nitrogen concentration strong variations that therefore adopts, promptly the impact resistance of this method is stronger.And the bioremediation that adopts conventional removal ammonia nitrogen needs cultured strain, initial failure period long, and the volume of biological reaction tank fixed, and when the ammonia nitrogen concentration strong variations, can't reach gratifying removal effect.
2, adopt and to carry out chlorination earlier and remove ammonia nitrogen, back interpolation can form material (quicklime/lime for example, the calcium hydroxide of water-fast Calcium Fluoride (Fluorspan) with fluorion; Calcium salts such as calcium chloride); Not only treatment effect is stable good, and the alkali that utilizes the material that need add in the defluorination operation process to produce neutralizes and denitrogenate the acid that produces in the reaction, helps the control of water outlet pH value; Reach best defluorination effect, and simple to operate.
3, the present invention is when operation; Not once to drop into chlorine; But divide two batches of addings, and so be convenient to follow-uply according to the different economy and the useful embodiment the most selected of fluorion in the waste water with the ratio of ammonia-nitrogen content, be convenient to the control of removal of ammonia and nitrogen process and improve the removal efficiency of ammonia nitrogen.
4, through in the waste water after the present invention's processing, content of fluoride ion and ammonia-nitrogen content all effectively reduce, and according to different environmental requirements, can discharge or further pass through manipulation of regeneration and carry out recycling.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing and concrete embodiment the present invention is done further detailed explanation, but the invention is not restricted to this.
Numerical value when following embodiment additive amount is season in spring and autumn.
Embodiment 1
The fluorine-containing nitrogen-containing wastewater of certain electronic industry contains pollutents such as a large amount of fluorine, ammonia nitrogen, organonitrogen, phosphorus and suspended solid, and the total dissolved solidss salts contg is higher in the water.The major pollution thing contains scale and sees table 1 for details in the concrete waste water.
Table 1: the principal pollutant of fluorine-containing nitrogen-containing wastewater contain scale
| Ammonia nitrogen | Total nitrogen | Fluorion | Ammonia nitrogen/fluorion | COD | SS | Phosphorus | TDS | The pH value |
| 20mg/L | 26mg/L | 55mg/L | 0.36 | 50mg/L | 50mg/L | 4.8mg/L | 2000mg/L | 6～9 |
As shown in Figure 1, make waste water remove the ammonia nitrogen processing through mainly carrying out defluorination successively by equalizing tank, reaction tank, settling pond and V-type silica sand filter tank.Concrete treatment process is following:
Above-mentioned wastewater treatment process is specific as follows:
(1), equalizing tank:, therefore the equilibrium that equalizing tank carries out the water quality and the water yield is set because all there is certain malconformation the water quality and the water yield aspect of discharging.
(2), reaction tank: waste water gets into the reaction tank that is provided with stirrer through the lift pump lifting and carries out chemistry except that the chemical reaction deposition of ammonia nitrogen operation, defluorination operation, the coagulating of defluorination operation, and is specific as follows:
1. according to the water quality characteristics of waste water; Adopt: ammonia nitrogen on-line monitoring instrument apparatus is installed in (1) on suction culvert with in the reaction tank; The real-time ammonia-nitrogen content in the monitoring waste water, monitoring result feeds back to system and in reaction tank, adds the amount of liquid chlorine with the control chlorinating machine, and divide two batches add liquid chlorine (press first about 70%; Second batch about 30% adds), be of value to the process control and the removal efficiency that improves ammonia nitrogen of removal of ammonia and nitrogen.Can solve because not enough not high problem and the chlorination of ammonia nitrogen efficient of removing of chlorination adds the too high problem of excessive chlorine residue, guarantee that effluent quality reaches the 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 the waste water.
2. because in the waste water; The ratio of ammonia nitrogen/content of fluoride ion was less than 1: 2.5; Then implement each above-mentioned reaction according to following process: add first time liquid chlorine earlier and remove the part ammonia nitrogen, add the calcium hydroxide that adds the liquid chlorine equivalent with first batch of institute again, on the one hand calcium hydroxide can in remove the hydrochloric acid of ammonia nitrogen generation with liquid chlorine; The calcium ion of calcium hydroxide can generate the Calcium Fluoride (Fluorspan) that is insoluble in water with the reaction of part fluorion on the other hand; Add second batch of liquid chlorine then and remove remaining ammonia nitrogen in the waste water, add the calcium hydroxide neutralization once more the pH value is controlled between 6.0～7.0, be beneficial to the formation of calcium fluoride crystal; Insufficient calcium ion part is replenished through adding calcium chloride again, finally can most fluorion be converted into Calcium Fluoride (Fluorspan).
3., under whipped state, add coagulating agent (Poly aluminum Chloride (PAC) PAC, SEPIGEL 305 PAM or the combination of the two) through the waste water after the above-mentioned steps.Because the Calcium Fluoride (Fluorspan) that subordinate phase defluorination reaction produces is insoluble fine particle, precipitable property is poor, can make the fine particle chemistry that comprises Calcium Fluoride (Fluorspan) take off steady and forms more big flocculating body, reinforced deposition effect through dosing coagulant.
Adopt above-mentioned additive and coagulation-settlement process can remove phosphorus simultaneously, the phosphorus in the waste water is removed through the settling pond deposition in reaction tank with behind the lime reaction generation calcium phosphate granules.
(3), settling pond: the water outlet of reaction tank precipitates after 1～2 hour from flowing into settling pond, and the most of fluorochemical in the waste water, suspended substance and partial organic substances deposition form mud discharging and remove.The mud of settling pond is transported to sludge dehydration device sludge dewatering is become mud cake, and mud cake contains calcium component, can be exploited, and is the good raw material of making the environmental protection fragment of brick, and storage basin supernatant and filtrating are back to the equalizing tank circular treatment.The upper strata supernatant is not higher than 9mg/L through detecting content of fluoride ion, and ammonia-nitrogen content is lower than 0.5mg/L, can make it from flowing into V-type silica sand filter.
(4), V-type silica sand filter tank, the supernatant liquid of settling pond is from flowing into the V-type filter tank of the quartz sand filter media layer of uniform grading, filtering velocity is controlled at 5.5～7.5m
3/ m
2Between the h, mainly be through failing settled fine suspension and gelatinoid in the physical filtering effect removal settling pond.When filtering layer after filter tank operation for some time stops up and when influencing filtering velocity, available air-water backwashing filtering layer recovery filtering velocity, rinse water are back to the equalizing tank circular treatment.Waste water through after this step process can carry out regeneration through ultra-filtration membrane equipment basically.
Take aforesaid method to have following characteristics:
1, the reaction times except that the ammonia nitrogen reaction only needs about 5～7 minutes.The time of fluorion and calcium ion reaction also only needs 5～7 minutes; Have conventional biological treatment remove the ammonia nitrogen method incomparable efficient, fast, and also overcome the following deficiency that the ammonia nitrogen method is removed in conventional biological treatment simultaneously: the biodegradability of (1) waste water own is poor; (2) adopt biological treatment to remove ammonia nitrogen, need supplementary carbon source, and there is high, inflammable, explosive, the uneasy congruent limitation of cost in carbon source such as methyl alcohol preferably; Problems such as (3) the biological treatment unit is complicated, and the land occupation resource is many, and construction cost is high, and the construction period is long, and processing efficiency is relatively low.
2, adopt chemical chlorination denitrogenation to remove the ammonia nitrogen in the waste water, reduced ammonia-nitrogen content effectively, quick, efficient, stable; When the ammonia nitrogen concentration variation range of water inlet is big, only need to change and add dose and just can reach treatment effect according to reaction ratio, the trade effluent of the chemical technology ability flexible adaptation ammonia nitrogen concentration strong variations that therefore adopts, promptly the impact resistance of this technology is stronger.And the bioremediation that adopts conventional removal ammonia nitrogen needs cultured strain, initial failure period long, and the volume of biological reaction tank fixed, and when the ammonia nitrogen concentration strong variations, can't reach gratifying removal effect.
Embodiment 2
The fluorine-containing nitrogen-containing wastewater of certain electronic industry contains pollutents such as a large amount of fluorine, ammonia nitrogen, organonitrogen, phosphorus and suspended solid, and the total dissolved solidss salts contg is higher in the water.The major pollution thing contains scale and sees table 2 for details in the concrete waste water.
Table 2: the principal pollutant of fluorine-containing nitrogen-containing wastewater contain scale
| Ammonia nitrogen | Total nitrogen | Fluorion | Ammonia nitrogen/fluorion | COD | SS | Phosphorus | TDS | The pH value |
| 25mg/L | 32mg/L | 50mg/L | 0.50 | 50mg/L | 50mg/L | 4.8mg/L | 2000mg/L | 6～9 |
According to the principle of the method for wastewater treatment of present embodiment with embodiment 1; But its concrete operating process is different; Specifically carry out according to following mode: add earlier first time liquid chlorine and remove the part ammonia nitrogen, add the calcium hydroxide that adds the liquid chlorine equivalent with first batch of institute again, on the one hand calcium hydroxide can in remove the hydrochloric acid of ammonia nitrogen generation with liquid chlorine; The calcium ion of calcium hydroxide can generate the Calcium Fluoride (Fluorspan) that is insoluble in water with the fluorion reaction on the other hand; Add second batch of liquid chlorine then and remove remaining ammonia nitrogen in the waste water, add remaining calcium hydroxide once more, the hydrogen make-up sodium oxide is controlled between 6.0～7.0 the pH value simultaneously; Be beneficial to the formation of calcium fluoride crystal, finally can most fluorion be converted into Calcium Fluoride (Fluorspan).
After the processing of present embodiment method, the content of fluoride ion in the waste water is not for being higher than 9mg/L, and ammonia-nitrogen content is lower than 0.5mg/L.
Embodiment 3
The fluorine-containing nitrogen-containing wastewater of certain electronic industry contains pollutents such as a large amount of fluorine, ammonia nitrogen, organonitrogen, phosphorus and suspended solid, and the total dissolved solidss salts contg is higher in the water.The major pollution thing contains scale and sees table 3 for details in the concrete waste water.
Table 3: the principal pollutant of fluorine-containing nitrogen-containing wastewater contain scale
| Ammonia nitrogen | Total nitrogen | Fluorion | Ammonia nitrogen/fluorion | COD | SS | Phosphorus | TDS | The pH value |
| 35mg/L | 43mg/L | 37mg/L | 0.95 | 50mg/L | 50mg/L | 4.8mg/L | 2000mg/L | 6～9 |
According to the principle of the method for wastewater treatment of present embodiment with embodiment 1; But its concrete operating process is different; Specifically carry out: add first time liquid chlorine earlier and remove the part ammonia nitrogen according to following mode; Add the calcium hydroxide and the sodium hydroxide that add the liquid chlorine equivalent with first batch of institute again, on the one hand calcium hydroxide can in remove the hydrochloric acid that ammonia nitrogen produces with liquid chlorine, the calcium ion of calcium hydroxide can be insoluble in the Calcium Fluoride (Fluorspan) of water with fluorion reaction generation on the other hand; Add second batch of liquid chlorine then and remove remaining ammonia nitrogen in the waste water; The hydrogen make-up sodium oxide is controlled between 6.0～7.0 the pH value simultaneously, is beneficial to the formation of calcium fluoride crystal, finally can most fluorion be converted into Calcium Fluoride (Fluorspan).
After the processing of present embodiment method, the content of fluoride ion in the waste water is not for being higher than 9mg/L, and ammonia-nitrogen content is lower than 0.5mg/L.
More than the present invention has been done detailed description; Its purpose is to let the personage that is familiar with this art can understand content of the present invention and implements; Can not limit protection scope of the present invention with this; All equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (7)
1. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry; Content of fluoride ion is for being not less than 20mg/L in the fluorine-containing nitrogen-containing wastewater of said electronic industry; Ammonia-nitrogen content is for being not less than 15mg/L, and pH is 6～9, it is characterized in that: the treating method comprises the following steps of carrying out successively:
(1), remove the ammonia nitrogen operation: in waste water, feeding oxidizer containing chlorine, to make ammonia nitrogen and oxidizer containing chlorine reaction conversion in the waste water be that nitrogen is removed, and said oxidizer containing chlorine is liquid state or gasiform Cl
2, and with 1mg/L ammonia nitrogen input 7.6～8.0mg/L Cl in the waste water
2Ratio in waste water, add Cl
2, wherein divide two batches to add Cl
2, wherein first batch of add-on is 65～75%, remaining second batch of adding adding first batch of Cl
2Afterwards, add and first batch of Cl that is added
2The alkali of equivalent with in and Cl
2With the hydrochloric acid of ammonia nitrogen reaction generation, and then add second batch of Cl
2
(2), defluorination operation: take the chemical reaction precipitation to separate the mode that combines with coagulating sedimentation; Wherein chemical reaction precipitation is to point to that to add the material of calcium ions in the waste water and under the condition of pH6～7, make the fluorine ion reaction conversion in the waste water be calcirm-fluoride; The material of said calcium ions is one or more the combination that is selected from calcium oxide, calcium hydroxide or the soluble calcium salt; And the ratio that drops into 2.3～2.5mg/L calcium ion with 1mg/L fluorine ion in the waste water is added the material of calcium ions in reaction tank; It is to instigate calcirm-fluoride chemistry under the effect of coagulant of generation to take off steady formation flco to strengthen sedimentation effect that said coagulating sedimentation separates; Leave by precipitation and moisture again
When the ratio of ammonia-nitrogen content in the fluorine-containing nitrogen-containing wastewater of described electronic industry and content of fluoride ion during less than 1: 2.5, in the step (1), the said alkali of adding is calcium hydroxide; In the step (2); In completing steps (1) waste water afterwards, add calcium hydroxide to regulate pH between 6～7; And then add soluble calcium salt, afterwards, under the state that stirs, add coagulating agent; Total input amount of the calcium hydroxide that wherein, is added in the step (1), the quicklime that step (2) is added and soluble calcium salt satisfies the proportion requirement that the 1mg/L fluorion drops into 2.3～2.5mg/L calcium ion in the waste water;
Ammonia-nitrogen content is 1: 1.75～2.5 with the ratio of content of fluoride ion in the fluorine-containing nitrogen-containing wastewater of described electronic industry, and in the step (1), the said alkali of adding is calcium hydroxide; In the step (2): in completing steps (1) waste water afterwards, add calcium hydroxide once more; Total input amount of the calcium hydroxide that adds in the calcium hydroxide of this time adding and the step (1) satisfies the proportion requirement that the 1mg/L fluorion drops into 2.3～2.5mg/L calcium ion in the waste water; Simultaneously; Adding sodium hydroxide adjusting wastewater pH is 6～7, and under whipped state, adds coagulating agent;
When the ratio of ammonia-nitrogen content in the fluorine-containing nitrogen-containing wastewater of described electronic industry and content of fluoride ion during greater than 1: 1.75; The material of said calcium ions is a calcium hydroxide; In step (1); Drop into the alkali of the hydrochloric acid that reaction produces with ammonia nitrogen in the required calcium hydroxide conduct of whole defluorinations, insufficient alkali is supplied with sodium hydroxide; In the step (2), in completing steps (1) waste water afterwards, adding sodium hydroxide, to regulate wastewater pH be 6～7, and at the state that stirs adding coagulating agent down.
2. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 1; It is characterized in that: step (1) and step (2) are all carried out in a reaction tank; After adding coagulating agent, make the water outlet of reaction tank obtain upper strata supernatant and the precipitating sludge that fluorinion concentration is not higher than 9mg/L in 1～2 hour from flowing into the settling pond deposition.
3. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 1 and 2 is characterized in that: said coagulating agent is Poly aluminum Chloride (PAC), SEPIGEL 305 or the combination of the two.
4. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 1 and 2 is characterized in that: said treatment process also further comprises step (3): the upper strata supernatant in the settling pond is filtered from flowing into the silica sand filter tank.
5. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 4 is characterized in that: said treatment process also comprises step (4): the mud that deposition in the settling pond is produced is processed into available mud cake with dewatering unit.
6. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 1; It is characterized in that: on suction culvert with in the reaction tank, ammonia nitrogen on-line monitoring instrument apparatus is installed; Monitor the ammonia-nitrogen content in the waste water in real time, monitoring result feeds back to system and in reaction tank, adds Cl in proportion with the control chlorinating machine
2
7. the treatment process of the fluorine-containing nitrogen-containing wastewater of electronic industry according to claim 6; It is characterized in that: fluorion on-line monitoring appearance and online pH meter also are installed in reaction tank; The pH value of content of fluoride ion and waste water in the real-time monitoring waste water; Monitoring result feeds back to system, and system adds the material of calcium ions according to content of fluoride ion in the waste water in waste water.
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| CN115323171A (en) * | 2022-08-31 | 2022-11-11 | 河南恒润科技有限公司 | Method for reducing content of fluorine ions in lithium carbonate production process |
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