CN110510813A - A kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry - Google Patents
A kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry Download PDFInfo
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- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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Abstract
The invention discloses a kind of processing methods of nitrogen-containing heterocycle compound wastewater from chemical industry, belong to field of waste water treatment.The present invention makes nitrogen heterocyclic open loop chain rupture, reduces bio-toxicity, heterocycle organic nitrogen is completely converted into ammonia nitrogen, avoids the sustained release of ammonia nitrogen during subsequent biological treatment by electrolysis generation trough and the combination pretreatment of cell reaction slot；It is handled in conjunction with anaerobic bio-treated and biological denitrificaion reaction system.Method of the invention has the advantages that strong load impact ability, easily operated control, operating cost are low, and especially having to nitrogen-containing heterocycle compound wastewater from chemical industry can good treatment effect.
Description
Technical field
The invention belongs to field of waste water treatment, more specifically to a kind of place of nitrogen-containing heterocycle compound wastewater from chemical industry
Reason method.
Background technique
Heterocyclic compound refers to the organic compound in molecule containing heterocycle structure, constitutes carbon atom in the atom of ring
Outside, also at least contain a hetero atom, the most common hetero atom is nitrogen-atoms, sulphur atom and oxygen atom.Heterocyclic compound is universal
It is present in the industries such as medication chemistry, dye chemical industry, and in numerous heterocyclic compounds most with the heterocyclic compound of nitrogen atom
It is common.
Nitrogen-containing heterocycle compound is poisonous and harmful biodegradable organic compounds mostly, and Nature comparison is stablized, in metabolic process
It is not easy to be destroyed, toxicity is big, and environmental pollution is serious and is detrimental to health.In addition, nitrogen-containing heterocycle compound not only cannot be by
Microorganism decomposition metabolism can also generate serious murder by poisoning and inhibiting effect to the metabolic process of microorganism.
Currently, nitrogen-containing heterocycle compound waste water treatment process mainly has: physical-chemical process, bioanalysis and advanced oxidation skill
Art.For physical-chemical process based on flocculating, removal rate is low, and the sludge quantity of generation is more, and dehydration is difficult, though eliminate venomous injurant
Matter, but pollutant has been transferred to solid phase from liquid phase, still needs to successive depths processing.The screening and culture of efficient degrading bacterial strain are biology
Method processing bio-refractory nitrogen heterocyclic provides theoretical basis, but bacterial strain has specificity, and not yet discovery can be same at present
When remove the bacterial strains of a variety of nitrogen-containing heterocycle compounds, the complexity and diversity of degradative pathway cause water-quality constituents more complicated, give up
Water toxicity is stronger.High-level oxidation technology can by organic matter permineralization, and have reaction speed it is fast, it is pollution-free, applied widely,
The advantages that at low cost.High-level oxidation technology mainly includes Fenton reagent oxidizing process, wet oxidation process, photocatalytic oxidation, smelly
Oxygen oxidizing process, supercritical oxidation process and Electrocatalytic Oxidation.
Publication No. CN105600880A is found through retrieval, and the Chinese invention patent application in date of publication on May 25th, 2016 is public
A kind of combination process for advanced treatment of nitrogen-containing heterocycle compound chemical industry tail water is opened, the invention is by electrochemical oxidation and UF membrane skill
Art, which combines, forms electrolemma coupling technique, and utilizes biological aerated filter degradation of organic substances and electrodialysis desalination, realizes each work
The optimization linking of section treatment process, makes each waste water treatment process reach optimum efficiency, and final outflow water content of organics COD≤
50mg/L, conductivity≤10 μ S/cm.But the complicated component of nitrogen-containing heterocycle compound wastewater from chemical industry, and have high COD, high saliferous,
The features such as high ammonia nitrogen, high total nitrogen, biochemical is poor and high chroma and high suspended matter；Therefore, for nitrogen-containing heterocycle compound waste water
These features, it is still necessary to further develop effective processing method.
Summary of the invention
1. to solve the problems, such as
For there are anti-load impact abilities in the existing nitrogen-containing heterocycle compound wastewater processing technology low, energy of resistance to bio-toxicity
The problems such as power is weak, treatment effect needs to be further increased, operating cost is high, the present invention provides a kind of nitrogen-containing heterocycle compound chemical industry
The processing method of waste water.The present invention pre-processes the suspended matter in removal waste water by coagulating sedimentation first, passes through electrolysis hair later
Raw slot electrolysis generates oxidant and reacts in cell reaction slot to reduce the bio-toxicity in waste water, and organic nitrogen is totally converted
At ammonia nitrogen, then enters anaerobic organism reaction system and remove organic matter, reduce COD, enter back into biological denitrificaion reaction system, degrade
Rest COD simultaneously removes total nitrogen.The present invention combines electrolytic oxidation pretreatment and biological treatment, and during electrolytic oxidation process
Combination electrolysis generation trough and cell reaction slot have good removal effect to nitrogen-containing heterocycle compound wastewater from chemical industry, and have
The anti-load impact ability of the system of enhancing.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
A kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry of the invention, comprising the following steps:
S10, so that waste water is entered coagulative precipitation tank progress coagulating kinetics, remove the suspended particulate substance in waste water, obtain
Waste water A；
S20, so that waste water A is entered electrolysis generation trough progress cell reaction, generate oxidant；Then enter cell reaction slot into
Row open loop processing, reduces the bio-toxicity of waste water, obtains waste water B；
S30, make waste water B enter biochemical conditioning tank to be adjusted, obtain waste water C；
S40, make waste water C enter anaerobic organism reaction system to be handled, removal organic matter simultaneously reduces COD, obtains waste water
D；
S50, make waste water D enter biological denitrificaion reaction system to be handled, remove remaining COD and remove total nitrogen, obtain
Water outlet that treated.
Preferably, in step S10, before making waste water enter coagulative precipitation tank, the pH of waste water is adjusted to 6~8.
Preferably, in step S20, residence time of the waste water A in electrolysis generation trough is less than to stop in cell reaction slot
Stay the time.
Preferably, further include that waste water B is back to electrolysis generation trough in step S30, carry out cell reaction.
Preferably, in step S40, anaerobic organism reaction system includes level-one anaerobic reactor and secondary anaerobic reactor.
Preferably, in step S50, biological denitrificaion reaction system include anoxic biological reaction pool, aerobe reaction pond and
Secondary settling tank.
Preferably, in step S20, residence time of the waste water A in electrolysis generation trough is 5~60min, in cell reaction slot
The interior residence time is 30~180min.
Preferably, the reflux ratio of waste water B is 100~300% in step S30.
Preferably, temperature adjusting is carried out to waste water before waste water B being back to electrolysis generation trough, the temperature of waste water is adjusted
It is 5~60 DEG C.
Preferably, the anode being electrolysed in generation trough is RuO2-IrO2/Ti、RuO2-IrO2-SnO2/ Ti and RuO2-IrO2-
SnO2-Sb2O5Any one of/Ti, cathode are any one of titanium plate, 316L stainless steel and graphite.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) processing method of a kind of nitrogen-containing heterocycle compound wastewater from chemical industry of the invention, by selection electrolytic oxidation to containing
Nitrogen heterocyclic wastewater from chemical industry is pre-processed, and by its open loop chain rupture, is reduced its bio-toxicity, is improved biodegradability；Lead to again
It crosses two-stage anaerobic bio-reaction system and removes most of organic loading, reduce subsequent processing burden, it is then anti-by biological denitrificaion
It answers system to reduce remaining organic loading and nitrogen load, improves system resistance to overload shock ability, reduce cost for wastewater treatment；
(2) processing method of a kind of nitrogen-containing heterocycle compound wastewater from chemical industry of the invention, by electrolytic oxidation in waste water
Nitrogen heterocyclic carry out effective open loop chain rupture, significantly reduce its bio-toxicity, nitrogen is most in heterocycle in electrolytic acid cleaning oxydation process
It is completely converted into ammonia nitrogen eventually, avoids the ammonia nitrogen sustained release in subsequent bio reaction process；
(3) a kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry of the invention, waste water are introduced into electrolysis generation trough,
Generate high activity oxide, then enter cell reaction slot to organic pollutant carry out open loop processing, using electrolysis generation trough and
The advantageous combination of cell reaction slot: high activity oxide generates place and reacting environment's separation, it can be achieved that independent control, operation spirit
It is living；In addition, high activity oxide sufficiently participates in the reaction of degradation of organic substances, avoids it after electrolysis generation trough and reactive tank
Toxic action to microorganism in subsequent biochemical system；
(4) processing method of a kind of nitrogen-containing heterocycle compound wastewater from chemical industry of the invention, passes through two-stage anaerobic biological respinse
System removes organic loading, and the pre-treatment that wherein level-one anaerobic reactor is reacted as secondary anaerobic has degradation electrolytic oxidation
The poisonous and harmful intermediate product generated in reaction process, reduces the bio-toxicity of waste water, improves the effect of wastewater biodegradability；
(5) processing method of a kind of nitrogen-containing heterocycle compound wastewater from chemical industry of the invention, passes through biological denitrificaion reaction system
In anoxic+aerobic process can effectively remove total nitrogen so that this method has biological nitration and denitrification function.
Detailed description of the invention
Fig. 1 is a kind of flow diagram of the processing method of nitrogen-containing heterocycle compound wastewater from chemical industry of the invention.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Embodiment 1
As shown in Figure 1, a kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry of the invention, specific steps are as follows:
S10, make the actual production wastewater collection of certain chemical company from production 4,6- dihydroxy-pyrimidine (DHP) in waste water
In collecting pit, the specific targets of the waste water quality are as shown in table 1 below.The pH of waste water is adjusted to 6~8, the present embodiment is
Waste water is then pumped into coagulative precipitation tank by pH7.5, coagulant is added into coagulative precipitation tank, flocculant carries out coagulating sedimentation
Processing obtains waste water A and sediment to remove the suspended particulate substance in waste water, and after sediment filter-press dehydration, it is heavy to obtain solid
Shallow lake waste and filtrate, filtrate are recycled in coagulative precipitation tank water inlet pipe, and circulation carries out the coagulating kinetics in coagulative precipitation tank；
S20, waste water A is made to sequentially enter electrolysis generation trough and cell reaction slot；It is anti-that electro-catalysis is carried out in electrolysis generation trough
It should be to generate the high activating oxides such as hydroxyl radical free radical, active oxygen, active oxychloride.Electrolysis generation trough in anode be
RuO2-IrO2/Ti、RuO2-IrO2-SnO2/ Ti and RuO2-IrO2-SnO2-Sb2O5Any one of/Ti, cathode be titanium plate,
Any one of 316L stainless steel and graphite；Electrolytic condition are as follows: current density is 200~1000A/m2, the residence time of waste water A
For 5~60min；The anode that generation trough is electrolysed in the present embodiment is RuO2-IrO2/ Ti, cathode are titanium plate, current density 350A/
m2, the residence time of waste water A is 45min；
Waste water A then containing highly reactive form of oxygen agent carries out electrolytic oxidation reaction in cell reaction slot, and waste water A is being electrolysed
Residence time in reactive tank is 30~180min, greater than the residence time in electrolysis generation trough；Cell reaction slot is high living
Property oxide with organic matter to be degraded provide the place sufficiently reacted, nitrogen-containing heterocycle compound is by open loop in cell reaction slot
It handles, nitrogen is finally completely converted into ammonia nitrogen in heterocycle, is reduced the bio-toxicity of waste water, is obtained waste water B；It gives up in the present embodiment
Residence time 120min of the water in cell reaction slot；
S30, make waste water B enter biochemical conditioning tank to be adjusted, obtain waste water C, and waste water B can also be made to be back to electricity
It solves generation trough and carries out cell reaction, to increase the mass transfer of system, to promote the efficiency of reaction；The reflux ratio of waste water B be 100~
300%, the reflux ratio of waste water B is 200% in the present embodiment；
It should be noted that needing to carry out temperature adjusting to waste water before waste water B to be back to electrolysis generation trough, returning
Heat-exchange system (heat exchanger) is provided on flow tube line, by heat exchanger by the lower water temperature of reflux to 5~60 DEG C, then with waste water
A is mixed into cell reaction slot, and recirculation water water temperature is 42 DEG C in the present embodiment.The effect being arranged in this way is to can be improved electrolysis
Cell reaction efficiency in generation trough and cell reaction slot extends electrode plate service life.
S40, make waste water C enter anaerobic organism reaction system to be handled, organic matter and reduce COD to remove；Wherein
Anaerobic organism reaction system includes level-one anaerobic reactor and secondary anaerobic reactor, and waste water C detests followed by firsts and seconds
Oxygen reactor, residence time of the waste water in level-one anaerobic reactor are 2~12h, when stop in secondary anaerobic reactor
Between for 8~for 24 hours, obtain waste water D and sludge, sludge is by sludge concentration tank processing, the supernatant and sludge pressure obtained after processing
Filter dehydration filtrate is back to biochemical conditioning tank and carries out homogeneous average；When waste water stops in level-one anaerobic reactor in the present embodiment
Between be 8h, in secondary anaerobic reactor the residence time be 22h；
It should be further noted that the level-one anaerobic reactor in anaerobic organism reaction system is reacted as secondary anaerobic
Pre-treatment, have that the intermediate product toxic to microorganism caused by degradation electrolytic oxidation reaction, to improve waste water biochemical
The effect of property.
S50, make waste water D enter biological denitrificaion reaction system to be handled, remaining COD and remove total nitrogen to remove；
Wherein biological denitrificaion reaction system includes anoxic biological reaction pool, aerobe reaction pond and secondary settling tank, and waste water D is followed by scarce
Oxygen biological reaction pool, aerobe reaction pond and secondary settling tank, the residence time in hypoxia response pond is 2~16h, in aerobic tank
The interior residence time is 6~48h, and residence time of the waste water in hypoxia response pond is 12h in the present embodiment, in aerobic tank
Residence time is 42h.Aerobic reaction tank water outlet and secondary settling tank sludge are back to anoxic pond water inlet end, and secondary clarifier effluent is processing
Water outlet afterwards, into discharge bay qualified discharge.Biological denitrificaion reaction system realizes total nitrogen by biochemical nitrification and denitrification
Effectively remove (specific treatment effect is as shown in table 2 below).
1 DHP of table produces waste water quality index
2 system effluent index of table
The water outlet that processing method through this embodiment is handled meets " integrated wastewater discharge standard " (GB8978-
1996) discharge standard (three-level discharge standard)；And the wastewater treatment operations of the present embodiment are simple, operating cost is low.
Embodiment 2
The basic content of the present embodiment is same as Example 1, the difference is that: the present embodiment is to certain pharmacy containing quinoline
Enterprise's production waste water is handled, and the specific targets of waste water quality are as follows:
3 pharmacy waste water water quality indicator of table
The present embodiment makes from certain pharmacy corporation production wastewater collection containing quinoline in wastewater collection pond, and by waste water
PH is adjusted to 6.0.Then waste water is pumped into coagulative precipitation tank and carries out coagulating kinetics, to remove the suspension in waste water
The removal of grain object, the waste water A after coagulating sedimentation sequentially enter electrolysis generation trough and cell reaction slot, the anode being electrolysed in generation trough
For RuO2-IrO2-SnO2/ Ti, cathode are graphite；Electrolytic condition are as follows: current density 1000A/m2, the residence time of waste water A is
15min；Residence time of the waste water A in cell reaction slot is 30min.Make waste water B enter biochemical conditioning tank to be adjusted, obtain
Waste water B can also be back to electrolysis generation trough and carry out cell reaction, the reflux ratio 300% of waste water B by waste water C；In addition, waste water B
It exchanges heat before being back to electrolysis generation trough through heat exchanger, the recirculation water water temperature after heat exchange is 60 DEG C.Then it is raw to enter anaerobism by waste water C
Object processing system, waste water in level-one anaerobic reactor the residence time be 6h, in secondary anaerobic reactor the residence time be
12h；The water outlet of anaerobic organism reaction system enters biological denitrificaion reaction system, the residence time 36h in biological denitrification system.This reality
Applying residence time of the waste water in hypoxia response pond in example is 8h, and the residence time in aerobic tank is 28h.Specific processing effect
Fruit is as shown in table 4 below.
4 system effluent index of table
The water outlet that processing method through this embodiment is handled meets " integrated wastewater discharge standard " (GB8978-
1996) discharge standard (three-level discharge standard).
Embodiment 3
The basic content of the present embodiment is same as Example 1, the difference is that: the present embodiment to certain coal chemical industry sewage at
Reason station oil separator+air bearing water outlet is handled, and oil separator+air bearing effluent quality specific targets are as follows:
Table 5 certain coal chemical industry oil separator+air bearing effluent quality index
The present embodiment makes wastewater collection in wastewater collection pond, and the pH of waste water is adjusted to 8.0.Then waste water is pumped into
Coagulating kinetics are carried out in coagulative precipitation tank, to remove the removal of the suspended particulate substance in waste water, it is useless after coagulating sedimentation
Water A sequentially enters electrolysis generation trough and cell reaction slot, and the anode being electrolysed in generation trough is RuO2-IrO2-SnO2-Sb2O5/ Ti,
Cathode is 316L；Electrolytic condition are as follows: current density 200A/m2, the residence time of waste water A is 60min；Waste water A is anti-in electrolysis
Answering the residence time in slot is 180min.Make waste water B enter biochemical conditioning tank to be adjusted, obtains waste water C, it can also be by waste water
B is back to electrolysis generation trough and carries out cell reaction, the reflux ratio 100% of waste water B；In addition, waste water B be back to electrolysis generation trough it
It is preceding through heat exchanger, recirculation water water temperature after heat exchange is 25 DEG C.Then waste water C enters anaerobic biological treatment, and waste water is in level-one
The residence time is 12h in anaerobic reactor, and the residence time is for 24 hours in secondary anaerobic reactor；Anaerobic organism reaction system goes out
Water enters biological denitrificaion reaction system, the residence time 64h in biological denitrification system, and waste water is in hypoxia response pond in the present embodiment
The interior residence time is 16h, and the residence time in aerobic tank is 48h.Waste water is as shown in table 6 below in each workshop section's treatment effect:
6 system effluent index of table
The water outlet that processing method through this embodiment is handled meets " integrated wastewater discharge standard " (GB8978-
1996) discharge standard (three-level discharge standard).
The embodiment of the present invention is described in detail above, as long as but the hair of the invention essentially without disengaging
Bright point and effect can be there are many kinds of deformations, this will be readily apparent to persons skilled in the art.Therefore, such change
Shape example is also integrally incorporated within protection scope of the present invention.
Claims (10)
1. a kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry, comprising the following steps:
S10, so that waste water is entered coagulative precipitation tank progress coagulating kinetics, remove the suspended particulate substance in waste water, obtain waste water
A；
S20, so that waste water A is entered electrolysis generation trough progress cell reaction, generate oxidant；Then enter cell reaction slot to be opened
Ring processing, reduces the bio-toxicity of waste water, obtains waste water B；
S30, make waste water B enter biochemical conditioning tank to be adjusted, obtain waste water C；
S40, make waste water C enter anaerobic organism reaction system to be handled, removal organic matter simultaneously reduces COD, obtains waste water D；
S50, make waste water D enter biological denitrificaion reaction system to be handled, remove remaining COD and remove total nitrogen, handled
Water outlet afterwards.
2. a kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry according to claim 1, it is characterised in that: step
In S10, before making waste water enter coagulative precipitation tank, the pH of waste water is adjusted to 6~8.
3. a kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry according to claim 1, it is characterised in that: step
In S20, residence time of the waste water A in electrolysis generation trough is less than the residence time in cell reaction slot.
4. a kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry according to claim 1, it is characterised in that: step
Further include that waste water B is back to electrolysis generation trough in S30, carries out cell reaction.
5. a kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry according to claim 1, it is characterised in that: step
In S40, anaerobic organism reaction system includes level-one anaerobic reactor and secondary anaerobic reactor.
6. a kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry according to claim 1, it is characterised in that: step
In S50, biological denitrificaion reaction system includes anoxic biological reaction pool, aerobe reaction pond and secondary settling tank.
7. a kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry according to claim 3, it is characterised in that: step
In S20, residence time of the waste water A in electrolysis generation trough is 5~60min, residence time in cell reaction slot is 30~
180min。
8. a kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry according to claim 4, it is characterised in that: step
The reflux ratio of waste water B is 100~300% in S30.
9. a kind of processing method of nitrogen-containing heterocycle compound wastewater from chemical industry according to claim 4, it is characterised in that: will give up
Water B carries out temperature adjusting to waste water before being back to electrolysis generation trough, and the temperature of waste water is adjusted to 5~60 DEG C.
10. according to claim 1 or a kind of processing of nitrogen-containing heterocycle compound wastewater from chemical industry described in any one of 3-4 or 7-9
Method, it is characterised in that: the anode in electrolysis generation trough is RuO2-IrO2/Ti、RuO2-IrO2-SnO2/ Ti and RuO2-IrO2-
SnO2-Sb2O5Any one of/Ti, cathode are any one of titanium plate, 316L stainless steel and graphite.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113087248A (en) * | 2019-12-23 | 2021-07-09 | 南京延长反应技术研究院有限公司 | System and method for treating wastewater in hydroxyquinoline production |
| CN114890633A (en) * | 2022-06-15 | 2022-08-12 | 苏州苏净环保工程有限公司 | Treatment system and method for organic wastewater generated in battery assembly in automobile industry |
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