CN104250052B - A kind of mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen - Google Patents
A kind of mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen Download PDFInfo
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- CN104250052B CN104250052B CN201310263367.8A CN201310263367A CN104250052B CN 104250052 B CN104250052 B CN 104250052B CN 201310263367 A CN201310263367 A CN 201310263367A CN 104250052 B CN104250052 B CN 104250052B
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Abstract
The present invention relates to a kind of mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen, after mutual-amido two polyaniline factory effluent carries out pH regulator, with Aniline Production waste water mixing homogeneous, the waste water added in homogeneous equalizing tank containing nitrate radical completes the adjustment of C/N ratio to composite waste in homogeneous equalizing tank and pH value, and then N is added in homogeneous equalizing tank, P nutritive salt, if more containing waste residue amount in the water outlet of homogeneous equalizing tank, then need to carry out precipitation-air-flotation process to the water outlet of homogeneous equalizing tank, then high-enriched organics contained in the water outlet of homogeneous equalizing tank is removed by anti-nitration reaction, the basicity finally utilizing denitrification process to produce carries out the ammonia nitrogen in the water outlet of nitration reaction removal anti-nitration reaction.Method of wastewater treatment of the present invention, effectively can reduce the organism in this waste water and ammonia nitrogen, and significantly cuts down the total amount of pollutant that mutual-amido two polyaniline production equipment discharges in environment, makes discharged wastewater met the national standard.
Description
Technical field
The present invention relates to the process of organic chemical waste water, is a kind of mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen specifically.Espespecially containing the mutual-amido two polyaniline waste water denitrification-nitrated organics removal of ammonia nitrogen and a method for ammonia nitrogen, described mutual-amido two polyaniline waste water is containing concentration formic acid and high.
Background technology
Along with the development of economic society, day by day soaring to the demand of rubber ingredients, mutual-amido two polyaniline, be also called 4-ADPA, 4-aminodiphenylamine, commodity are called 4-aminodiphenylamine, as the intermediate of rubber ingredients, be a kind of important dyestuff and rubber ingredients intermediate, its main application is for producing p phenylenediamine type antioxidant (such as: rubber antioxidant 4010NA, 4020,4010 etc.).At present in Tire production industry, only 4010NA and 4,020 two kind of product, just occupies more than 70% of anti-aging agent total amount.Along with the development of automotive industry, the market requirement of p phenylenediamine type antioxidant constantly increases.The synthesis technique of domestic and international existing mutual-amido two polyaniline has more than 10 to plant, and the operational path for suitability for industrialized production mainly contains 4 kinds at present: aniline process, pentanoic method, formylaniline method and nitrobenzene method.
Domesticly at present have 8 enterprises and produce mutual-amido two polyanilines, wherein 7 all adopt formylaniline method route.The method Production Flow Chart is long, and formic acid consumption is large, containing a large amount of ammonia nitrogen in the factory effluent of one of its raw material aniline, causes containing concentration formic acid and high, ammonia nitrogen in the composite waste of plant emissions, and part benzene compounds.Therefore, the composite waste that such mutual-amido two polyaniline produces discharge has the features such as high chroma, high COD, high ammonia nitrogen, high salt, high ph-values, waste component is complicated, be difficult to direct biochemical treatment, therefore first through pre-treatment, waste water must be diluted, reduce Pollutant levels, and then carry out biochemical degradation or other secondary end-o f-pipe-control, to realize qualified discharge.
Chinese patent CN101492193A discloses a kind of method that process contains formaldehyde and formic acid wastewater, the method first allocates inorganic base aqueous solution, at high temperature pass into chlorine, the sodium chlorate aqueous solution made is joined in the trade effluent containing formaldehyde, formic acid, make formaldehyde, formic acid oxidized rapidly by reaction, and in reaction solution, add salt acid for adjusting pH value, realize the major part removal of formaldehyde, formic acid.According to this patent, the trade effluent containing formaldehyde, formic acid is made into inorganic base aqueous solution, passes into chlorine reaction for some time, and add salt acid for adjusting pH value, most of formaldehyde and formic acid are oxidized to carbonic acid gas removing.Although the method that this patent proposes significantly can reduce the COD of trade effluent, COD can be reduced to 1378mg/L from 9416mg/L, and COD clearance is 85.4%, and formic acid clearance is 90%.But the method also exists some problems below: first, chlorine is constantly passed in the process of inorganic base aqueous solution and have part chlorine gas leakage unavoidably in the middle of air, easily cause atmospheric pollution; Secondly, after the method process, in waste water, COD content not yet reaches discharging standards; Moreover whether also containing other pollutent in the waste water after process, this patent is also not mentioned.In brief, the simple the method that relies on also is difficult to the qualified discharge problem effectively solved containing formic acid factory effluent.
Chinese patent CN101200423 discloses a kind of method of epoxy ester waste water recycling device, this waste water is in acid, principal pollutant are formic acid, its process program is: first by epoxy soybean oil waste water oil removal process, then waste water is sent in reactor and under agitation add calcium carbonate, utilize calcium hydroxide emulsion regulator solution pH to 6 ~ 8, add precipitation agent removal heavy metal impurity again, remove solid impurity by the precipitator method and filter core method, finally filtrate evaporative crystallization, centrifugation and air stream drying are obtained formic acid product.According to this patent, the formic acid wastewater produced from epoxy soybean oil is introduced into oil trap, and grease floats up to surface, and lower floor's formic acid water delivers to equalizing tank through automatic bailer, reacts generate calcium formiate with pearl filler, the CO that reaction generates
2reclaiming purifies forms product; Containing a large amount of solid impurity in calcium formate solution crude product, therefore need to add quantitative PAC(polymerize aluminum chloride) coagulating agent, control hydraulic detention time 1 ~ 10h, fully form flocculation sediment after effect, drain into sludge sump by shore pipe; Calcium formate solution out enters next retort afterwards from settling tank, further with calcium carbonate reaction, is removed by residual formic acid; Add Na wherein afterwards
2s(sodium sulphite) and PAC coagulating agent.There are some problems below in the method: first, although illustrate the recovery process of formic acid in waste water in this patent, and whether waste water is after treatment containing other pollutent, and this patent is also not mentioned; Secondly, it is very loaded down with trivial details that the method reclaims formic acid technique, not only needs many group reactions device to leak to prevent too much formic acid to precipitate calcium formiate, and will fill into multiple as Na during the course
2the outer adding medicine such as S and PAC, adds processing cost.
In sum, the physico-chemical process adopted in prior art is large to carrying out pre-treatment power consumption containing formic acid factory effluent, and chemical oxidization method needs to add chemical oxidizing agent and reaches the object of disposing of sewage, and sewage disinfection treatment cost is higher.And the waste water recycling point proposed also is only principle, as need the waste water of discharge especially poisonous the or difficult degradation of high density waste water this how to process, substantially do not mention.Also lack at present and can effectively remove containing method organic in formic acid wastewater, want the qualified discharge realized containing ammonia nitrogen mutual-amido two polyaniline factory effluent still to lack complete effective means.
Summary of the invention
For the defect existed in prior art, the object of the present invention is to provide a kind of mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen, effectively can reduce the organism in this waste water and ammonia nitrogen, and significantly cut down the total amount of pollutant that mutual-amido two polyaniline production equipment discharges in environment, make discharged wastewater met the national standard.
For reaching above object, the technical scheme that the present invention takes is:
A kind of mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen, it is characterized in that, the described mutual-amido two polyaniline factory effluent containing ammonia nitrogen, for the mutual-amido two polyaniline factory effluent containing formic acid that produces in mutual-amido two polyaniline production process and the composite waste of Aniline Production waste water containing ammonia nitrogen, treatment step is as follows:
First pH regulator is carried out to the mutual-amido two polyaniline factory effluent containing formic acid, and then with containing the Aniline Production waste water mixing homogeneous of ammonia nitrogen, the waste water added in homogeneous equalizing tank containing nitrate radical completes the adjustment of C/N ratio to composite waste in homogeneous equalizing tank and pH value, and then N is added in homogeneous equalizing tank, P nutritive salt, if more containing waste residue amount in the water outlet of homogeneous equalizing tank, then need to carry out precipitation-air-flotation process to the water outlet of homogeneous equalizing tank, then high-enriched organics contained in the water outlet of homogeneous equalizing tank is removed by anti-nitration reaction, the basicity finally utilizing denitrification process to produce carries out the ammonia nitrogen in the water outlet of nitration reaction removal anti-nitration reaction, to realize discharged wastewater met the national standard.
On the basis of technique scheme, described containing formic acid and the water quality of composite waste containing ammonia nitrogen as follows: mutual-amido two polyaniline factory effluent pH is 10 ~ 13, COD is 50000 ~ 100000mg/L, TOC is 30000 ~ 60000mg/L, mainly contain organic pollutants in mutual-amido two polyaniline factory effluent to comprise: formic acid, aniline, phenol and p-nitrophenol, wherein said formic acid content is 114000 ~ 250000mg/L; In nitrogen-containing wastewater, ammonia nitrogen concentration is 200 ~ 350mg/L.
On the basis of technique scheme, its concrete treatment step is:
The first step, the mutual-amido two polyaniline factory effluent containing formic acid enters pH regulator pond, is adjusted to 4.5 ~ 6.0 with acid to its pH value;
Second step, the mutual-amido two polyaniline factory effluent containing formic acid of pH value has been regulated to enter homogeneous equalizing tank, with the Aniline Production waste water mixing homogeneous containing ammonia nitrogen in homogeneous equalizing tank, backward homogeneous equalizing tank in add nitrate solutions or provide the raw material required for denitrification containing the waste water of nitrate radical, and add and regulate composite waste pH value to 6.0 ~ 9.0 in homogeneous equalizing tank from the alkaline denitrification recirculation water of USB reactor and dilution water, homogeneous equalizing tank water outlet COD is 1000 ~ 2000mg/L, and ammonia nitrogen concentration is 100 ~ 200mg/L;
3rd step, adds N nutritive salt, P nutritive salt in homogeneous equalizing tank, to ensure that subsequent biochemical process is to N, P trace element demand;
4th step, if the waste residue amount contained in the water outlet of homogeneous equalizing tank is more, then the water outlet of homogeneous equalizing tank enters air flotation pool and carries out air supporting precipitation process, otherwise skips over this step;
5th step, delivers to USB reactor by the water outlet of homogeneous equalizing tank or the water outlet of air flotation pool and carries out anoxic denitrification reaction;
6th step, delivers to aerobic reactor by the water outlet of USB reactor and carries out aerobic nitrification reaction, and aerobic reactor water outlet COD is less than 80mg/L, and ammonia nitrogen is less than 15mg/L, reaches industrial wastewater discharge standard.
On the basis of technique scheme, described in the first step, acid is HCl or HNO
3.
On the basis of technique scheme, by regulating the add-on of nitrate radical to make homogeneous equalizing tank TOC of yielding water/NO in second step
3 --N ratio is 2.0 ~ 5.0, occurs accumulation and ensure that denitrification process is to the demand of nitrate radical to prevent anti-nitration reaction Nitrite.
On the basis of technique scheme, the nitrate solutions described in second step is sodium nitrate solution, and the waste water containing nitrate radical described in second step is ammonium nitrate wastewater or nitric acid portion tail magnesium water.
On the basis of technique scheme, in second step by regulate alkaline denitrification recirculation water control of reflux ratio homogeneous equalizing tank in composite waste pH 6.5 ~ 8.0.
On the basis of technique scheme, described in the 3rd step, N nutritive salt is urea, adds in waste water and makes its concentration to 90 ~ 100mg/L; P nutritive salt is potassium primary phosphate, with PO
4 3-meter, adds in waste water and makes its concentration to 3 ~ 5mg/L.
On the basis of technique scheme, the controling parameters carrying out anoxic denitrification process described in the 5th step in USB reactor is as follows: COD Inlet and outlet water volumetric loading is 3.5 ~ 5.7kg/m
3d, TOC Inlet and outlet water volumetric loading is 2.0 ~ 3.5kg/m
3d, formic acid Inlet and outlet water volumetric loading is 8.0 ~ 16.0kg/m
3dissolved oxygen in d, USB reactor is less than 0.50mg/L, and anoxic denitrification temperature controls at 19 ~ 36 DEG C.
On the basis of technique scheme, the temperature of reaction of the reaction of aerobic nitrification described in the 6th step controls at 22 ~ 36 DEG C, and in aerobic reactor, dissolved oxygen is greater than 2mg/L.
Mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen of the present invention, rational technology, easy to operate, effectively can remove organism and ammonia nitrogen in the mutual-amido two polyaniline factory effluent containing ammonia nitrogen, realize standard water discharge discharge.Treatment process less investment of the present invention, income are high, easy and simple to handle, treatment effect is stablized, and the waste water produced can processing and utilizing further, has both reached the object of reduction of discharging waste water, and has turn improved economic benefit.
Method of the present invention, denitrification process effectively can reduce COD and the formic acid content of waste water, and can provide basicity for follow-up nitrifying process, and in waste water, benzene compounds can effectively be removed simultaneously, medicament needed for whole treating processes is little, greatly can reduce treatment cost.The method has following beneficial effect:
(1) formic acid removal efficiency is high: formic acid clearance can reach 95 ~ 100%.
(2) formic acid volumetric loading is high: formic acid Inlet and outlet water volumetric loading reaches as high as 16kg/ (m
3d).
(3) containing the mutual-amido two polyaniline factory effluent of formic acid after denitrification process, create certain alkali number while greatly reducing waste water COD, this part alkali number can be used for supplying follow-up nitration reaction, reduces running cost.
(4) ammonia nitrogen removal efficiency is high: ammonia nitrogen removal frank is higher than 98%.
(5) cost is low: utilize the waste water of inside, chemical plant containing nitrate radical, or add a small amount of nitric acid, greatly can reduce processing cost.
(6) adopt USB reactor, utilize cotton-shaped denitrification sludge treatment containing the mutual-amido two polyaniline factory effluent of ammonia nitrogen, take up an area few.
Accompanying drawing explanation
The present invention has following accompanying drawing:
Fig. 1 process flow diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Waste water handled by the present invention is the mutual-amido two polyaniline factory effluent containing ammonia nitrogen, and this is a kind of composite waste, wherein:
(1) mutual-amido two polyaniline raw materials for production are formic acid and aniline, containing concentration formic acid and high in the mutual-amido two polyaniline factory effluent produced.
(2) ammonia nitrogen is had at the production Raw of aniline, so Aniline Production waste water is containing ammonia nitrogen in high density.
Therefore, the mutual-amido two polyaniline factory effluent containing ammonia nitrogen handled in the present invention, it is the composite waste of two strands of waste water, it comprises: mutual-amido two polyaniline factory effluent (containing concentration formic acid and high) and Aniline Production waste water (containing ammonia nitrogen in high density), and these two strands of waste water need carry out mixing homogeneous in homogeneous equalizing tank.Two kinds of waste water are distinguished and are treated by the present invention, mainly because different with the extension rate of ammonia nitrogen to organic concentration (e.g.COD) in operation, need dilute 45 ~ 55 times (preferably 50 times) organism, dilution 1.5 ~ 2.5 times (preferably 2 times) is only needed to ammonia nitrogen.So the COD and ammonia nitrogen concentration that enter USB reactor need be limited.
Mutual-amido two polyaniline factory effluent containing ammonia nitrogen of the present invention, for the mutual-amido two polyaniline factory effluent containing formic acid that produces in mutual-amido two polyaniline production process and the composite waste of Aniline Production waste water containing ammonia nitrogen, should be as follows containing the water quality of formic acid and the composite waste containing ammonia nitrogen: mutual-amido two polyaniline factory effluent pH is 10 ~ 13, COD is 50000 ~ 100000mg/L, TOC is 30000 ~ 60000mg/L, mainly contain organic pollutants in mutual-amido two polyaniline factory effluent to comprise: formic acid, aniline, phenol and p-nitrophenol, wherein said formic acid content is 114000 ~ 250000mg/L, in nitrogen-containing wastewater, ammonia nitrogen concentration is 200 ~ 350mg/L.
Mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen of the present invention, treatment step is as follows:
First pH regulator is carried out to the mutual-amido two polyaniline factory effluent containing formic acid, and then with containing the Aniline Production waste water mixing homogeneous of ammonia nitrogen, the waste water (or solution) added in homogeneous equalizing tank containing nitrate radical completes the adjustment of C/N ratio (carbon-nitrogen ratio) to composite waste in homogeneous equalizing tank and pH value, and then N is added in homogeneous equalizing tank, P nutritive salt, if more containing waste residue amount in the water outlet of homogeneous equalizing tank, then need to carry out precipitation-air-flotation process to the water outlet of homogeneous equalizing tank, then high-enriched organics (organism is formic acid mainly) contained in the water outlet of homogeneous equalizing tank is removed by anti-nitration reaction, the basicity finally utilizing denitrification process to produce carries out the ammonia nitrogen in the water outlet of nitration reaction removal anti-nitration reaction, to realize discharged wastewater met the national standard.
As shown in Figure 1, its concrete steps are:
The first step, the mutual-amido two polyaniline factory effluent containing formic acid enters pH regulator pond, is adjusted to 4.5 ~ 6.0 with acid to its pH value; Such as adjust ph is 4.5,5.0,5.5 or 6.0, be that neutrality is more wayward owing to regulating waste water ph in industrial operation, therefore should control in slant acidity containing the pH scope of mutual-amido two polyaniline factory effluent of formic acid in this step, to ensure that denitrification water outlet can not be too high and containing a certain amount of basicity;
Second step, the mutual-amido two polyaniline factory effluent containing formic acid of pH value has been regulated to enter homogeneous equalizing tank, with the Aniline Production waste water mixing homogeneous containing ammonia nitrogen in homogeneous equalizing tank, backward homogeneous equalizing tank in add nitrate solutions or provide the raw material required for denitrification containing the waste water of nitrate radical, and add and regulate composite waste pH value to 6.0 ~ 9.0 in homogeneous equalizing tank from the alkaline denitrification recirculation water of USB reactor and dilution water (such as tap water), such as adjust ph is 6.0,6.5,7.0,7.5,8.0,8.5 or 9.0; Homogeneous equalizing tank water outlet COD is 1000 ~ 2000mg/L, and ammonia nitrogen concentration is 100 ~ 200mg/L; The proportioning of the mutual-amido two polyaniline factory effluent containing formic acid and the Aniline Production waste water containing ammonia nitrogen is not limit (reason is that the ammonia nitrogen concentration of mutual-amido two polyaniline waste water COD and ammonia nitrogen waste water respectively has its own concentration range value), can adjust according to the different situations of reality, but should guarantee to dilute rear homogeneous equalizing tank water outlet COD and ammonia nitrogen concentration;
Homogeneous equalizing tank TOC of yielding water/NO is made by regulating the add-on of nitrate radical
3 --N ratio is 2.0 ~ 5.0, and in span, every increasing or decreasing 0.1 all can be used as a selectable specific embodiment, occurs accumulation and ensure that denitrification process is to the demand of nitrate radical to prevent anti-nitration reaction Nitrite;
3rd step, adds N nutritive salt, P nutritive salt in homogeneous equalizing tank, to ensure that subsequent biochemical process is to N, P trace element demand;
4th step, if the waste residue amount contained in the water outlet of homogeneous equalizing tank is more, then the water outlet of homogeneous equalizing tank enters air flotation pool and carries out air supporting precipitation process, otherwise skips over this step; The object of air supporting precipitation process removes suspended substance, colloid substances and the cotton-shaped particulate matter in the water outlet of homogeneous equalizing tank, and the oiliness foam to produce in acid-base neutralisation process in early stage, the oil slick that air supporting precipitation process produces and waste residue then can treatment measures be further processed routinely, no longer describe in detail; The judgement of waste residue amount can be implemented according to existing known technology, or rule of thumb judges, such as: no matter waste residue amount is many and few all carry out air supporting precipitation process etc., no longer describe in detail;
5th step, delivers to USB reactor by the water outlet of homogeneous equalizing tank or the water outlet of air flotation pool and carries out anoxic denitrification reaction;
6th step, delivers to aerobic reactor by the water outlet of USB reactor and carries out aerobic nitrification reaction, and aerobic reactor water outlet COD is less than 80mg/L, and ammonia nitrogen is less than 15mg/L, reaches industrial wastewater discharge standard, can qualified discharge.
In the present invention, organism in USB reactor in waste water, mainly formic acid, at denitrifying microorganism, (microorganism participating in anti-nitration reaction is multiple-microorganism mixing, can implement by prior art) effect under there is anti-nitration reaction, can remove the most of organism in waste water, remaining a small amount of organism can continue degraded and remove in aerobic reactor, and the ammonia nitrogen simultaneously in waste water is effectively removed by aerobic nitrification reaction.
On the basis of technique scheme, described in the first step, acid is HCl(hydrochloric acid) or HNO
3(nitric acid).
On the basis of technique scheme, the nitrate solutions described in second step is sodium nitrate solution, and the waste water containing nitrate radical described in second step is ammonium nitrate wastewater or nitric acid portion tail magnesium water.Described " nitric acid portion tail magnesium water " derives from the waste water that magnesium nitric acid process produces concentrated nitric acid technique, and in waste water, nitrogen (N) overwhelming majority exists with the form of nitrate radical.
On the basis of technique scheme, by composite waste pH value in the control of reflux ratio homogeneous equalizing tank of the alkaline denitrification recirculation water of adjustment in second step; PH value is preferably adjusted to 6.5 ~ 8.0.
On the basis of technique scheme, described in the 3rd step, N nutritive salt is urea, adds in waste water and makes its concentration to 90 ~ 100mg/L, and in span, every increasing or decreasing 1mg/L all can be used as a selectable specific embodiment; P nutritive salt is potassium primary phosphate, with PO
4 3-meter (in phosphate anion), add in waste water and make its concentration to 3 ~ 5mg/L, in span, every increasing or decreasing 0.5mg/L all can be used as a selectable specific embodiment.By the dosage of flow control N and P salt, do not carry out concrete mensuration.
On the basis of technique scheme, the controling parameters carrying out anoxic denitrification process described in the 5th step in USB reactor is as follows:
COD Inlet and outlet water volumetric loading is 3.5 ~ 5.7kg/m
3d, in span, every increasing or decreasing 0.1 all can be used as a selectable specific embodiment,
TOC Inlet and outlet water volumetric loading is 2.0 ~ 3.5kg/m
3d, in span, every increasing or decreasing 0.1 all can be used as a selectable specific embodiment,
Formic acid Inlet and outlet water volumetric loading is 8.0 ~ 16.0kg/m
3d, in span, every increasing or decreasing 1 all can be used as a selectable specific embodiment,
Dissolved oxygen in USB reactor is less than 0.50mg/L,
Anoxic denitrification temperature should control at 19 ~ 36 DEG C, and in span, every increasing or decreasing 1 DEG C all can be used as a selectable specific embodiment.
On the basis of technique scheme, the temperature of reaction of the reaction of aerobic nitrification described in the 6th step controls at 22 ~ 36 DEG C, and in span, every increasing or decreasing 1 DEG C all can be used as a selectable specific embodiment, and in aerobic reactor, dissolved oxygen is greater than 2mg/L.
Compared with prior art, the present invention has following characteristics:
(1) containing concentration formic acid and high and a certain amount of benzene compounds in the mutual-amido two polyaniline factory effluent processed in the present invention, COD is high, and pH value is high, and as adopted, physical chemistry method recovery formic acid process is very complicated and cost is very high.
(2) contriver is found by research, adopts conventional anaerobic biological technical finesse mutual-amido two polyaniline factory effluent, and organism processing load is difficult to improve, and anaerobic reaction limited efficiency, formic acid Inlet and outlet water volumetric loading is less than 7.0kg/m
3d.And the present invention adopts USB reactor to carry out this waste water of anoxic denitrification process, make use of the trade effluent containing nitrate radical on the one hand, saved water resources, realized the comprehensive utilization of waste water; Substantially increase organism processing load on the other hand, the Inlet and outlet water volumetric loading of process formic acid reaches as high as 16.0kg/m
3d.
(3) the present invention utilize USB reactor denitrification process mutual-amido two polyaniline production equipment waste water to have organics removal efficiency is high, processing load is high, energy consumption is low, hydraulic detention time is short, effluent quality is good, sludge yield is few, mud recoverable amount advantages of higher in reactor.Meanwhile, the basicity that denitrification process produces can be used for the aerobic nitrification reaction of follow-up ammonia nitrogen, reduces processing cost.Therefore, this method of wastewater treatment can as the process means of the mutual-amido two polyaniline waste water containing ammonia nitrogen, and guarantee that waste water organic pollutant content after this pre-treatment significantly reduces, ammonia nitrogen is effectively degraded, and waste water can reach sewage drainage standard.
It is below specific embodiment.
Embodiment 1
Certain chemical plant mutual-amido two polyaniline production equipment wastewater flow is 100t/d, and Pollutants in Wastewater index is: waste water COD is 50130mg/L, TOC is 30320mg/L, and formic acid concn is 116300mg/L, pH is 10.8; In nitrogen-containing wastewater, ammonia nitrogen concentration is 212mg/L.
The first step, in pH regulator pond, regulates mutual-amido two polyaniline wastewater pH to 4.5 with rare HCl.
Second step, at homogeneous equalizing tank, mutual-amido two polyaniline waste water (the mutual-amido two polyaniline factory effluent containing formic acid) mixes with nitrogen-containing wastewater (the Aniline Production waste water containing ammonia nitrogen), add the nitric acid portion tail magnesium water containing nitrate radical, and add USB reactor part recycling effluent and a small amount of dilution water dilutes waste water.In the water outlet of homogeneous equalizing tank, pH is 6.5, COD be 1002.6mg/L, TOC is 606.4mg/L, and formic acid is 2326.0mg/L, and nitrate radical is 1278.8mg/L, and ammonia nitrogen concentration is 106mg/L.TOC/NO in waste water
3 --N ratio maintains about 2.1
3rd step, adds urea concentration to 90mg/L in waste water, adds biphosphate potassium concn to 4mg/L(with PO
4 3-meter).
4th step, waste water gravity flow enters air flotation pool, removes suspended substance, colloid substances and cotton-shaped particulate matter in waste water further, and the oiliness foam produced in acid-base neutralisation process in early stage.
5th step, the waste water after precipitation-air-flotation enters USB reactor, and temperature of reaction is 19 DEG C.
6th step, USB water outlet enters aerobic reactor, and temperature of reaction is 22 DEG C.
The water quality situation of water outlet after denitrification-nitration treatment is as follows: pH is 7.3, COD be 76.2mg/L, TOC is 36.4mg/L, and formic acid content is 116.3mg/L, and ammonia nitrogen is 10.2mg/L, then COD Inlet and outlet water volumetric loading is 3.5kg/m
3d, TOC Inlet and outlet water volumetric loading is 2.2kg/m
3d, formic acid Inlet and outlet water volumetric loading is 8.4kg/m
3d, ammonia nitrogen Inlet and outlet water volumetric loading is 0.36kg/m
3d.
Embodiment 2
The mutual-amido two polyaniline production equipment wastewater flow in certain chemical plant is 110t/d, and Pollutants in Wastewater index is: waste water COD is 62400mg/L, TOC is 41700mg/L, and formic acid concn is 162600mg/L, pH is 11.4; In nitrogen-containing wastewater, ammonia nitrogen concentration is 276mg/L.
The first step, in pH regulator pond, regulates mutual-amido two polyaniline wastewater pH to 4.8 with rare HCl.
Second step, at homogeneous equalizing tank, mutual-amido two polyaniline waste water mixes with nitrogen-containing wastewater, adds the ammonium nitrate wastewater containing nitrate radical, and adds USB reactor part recycling effluent and a small amount of dilution water dilutes waste water.In the water outlet of homogeneous equalizing tank, pH is 7.1, COD be 1248.0mg/L, TOC is 834.0mg/L, and formic acid is 3252.0mg/L, and nitrate radical is 1273.6mg/L, and ammonia nitrogen concentration is 138mg/L.TOC/NO in waste water
3 --N ratio maintains about 2.9.
3rd step, adds urea concentration to 95mg/L in waste water, biphosphate potassium concn to 5mg/L(with PO
4 3-meter).
4th step, waste water gravity flow enters air flotation pool, removes suspended substance, colloid substances and cotton-shaped particulate matter in waste water further, and the oiliness foam produced in acid-base neutralisation process in early stage.
5th step, the waste water after precipitation-air-flotation enters USB reactor, and temperature of reaction is 27.6 DEG C.
6th step, USB water outlet enters aerobic reactor, and temperature of reaction is 28 DEG C.
The water quality situation of water outlet after denitrification-nitration treatment is as follows: pH is 7.5, COD be 67.4mg/L, TOC is 41.7mg/L, and formic acid content 130.1mg/L, ammonia nitrogen is 12.7mg/L, then COD Inlet and outlet water volumetric loading is 3.5kg/m
3d, TOC Inlet and outlet water volumetric loading is 2.4kg/m
3d, formic acid Inlet and outlet water volumetric loading is 9.4kg/m
3d, ammonia nitrogen Inlet and outlet water volumetric loading is 0.38kg/m
3d.
Embodiment 3
The mutual-amido two polyaniline production equipment wastewater flow in certain chemical plant is 120t/d, and Pollutants in Wastewater index is: waste water COD is 71500mg/L, TOC is 52620mg/L, and formic acid concn is 228700mg/L, pH is 12.5; In nitrogen-containing wastewater, ammonia nitrogen concentration is 325mg/L.
The first step, in pH regulator pond, uses rare HNO
3regulate mutual-amido two polyaniline wastewater pH to 5.4.
Second step, at homogeneous equalizing tank, mutual-amido two polyaniline waste water mixes with nitrogen-containing wastewater, adds sodium nitrate solution, and adds USB reactor part recycling effluent and a small amount of dilution water dilutes waste water.In the water outlet of homogeneous equalizing tank, pH is 7.2, COD be 1430.0mg/L, TOC is 1052.4mg/L, and formic acid is 4574.0mg/L, and nitrate radical is 1259.6mg/L, and ammonia nitrogen concentration is 162.5mg/L.TOC/NO in waste water
3 --N ratio maintains about 3.7.
3rd step, adds urea concentration to 98mg/L in waste water, biphosphate potassium concn to 3mg/L(with PO
4 3-meter).
4th step, this waste water and dregs amount is less, omits air supporting precipitation, by means of only air supporting settling tank.
5th step, waste water enters USB reactor, and temperature of reaction is 30.5 DEG C.
6th step, USB water outlet enters aerobic reactor, and temperature of reaction is 30 DEG C.
The water quality situation of water outlet after denitrification-nitration treatment is as follows: pH is 7.5, COD be 68.6mg/L, TOC is 42.1mg/L, and formic acid content 45.7mg/L, ammonia nitrogen is 12.6mg/L, then COD Inlet and outlet water volumetric loading is 4.8kg/m
3d, TOC Inlet and outlet water volumetric loading is 3.5kg/m
3d, formic acid Inlet and outlet water volumetric loading is 15.8kg/m
3d, ammonia nitrogen Inlet and outlet water volumetric loading is 0.52kg/m
3d.
Embodiment 4
The mutual-amido two polyaniline production equipment wastewater flow in certain chemical plant is 150t/d, and Pollutants in Wastewater index is: waste water COD is 97640mg/L, TOC is 59170mg/L, and formic acid concn is 248500mg/L, pH is 13.0; In nitrogen-containing wastewater, ammonia nitrogen concentration is 350mg/L.
The first step, in pH regulator pond, regulates mutual-amido two polyaniline wastewater pH to 6.0 with rare HCl.
Second step, at homogeneous equalizing tank, mutual-amido two polyaniline waste water mixes with nitrogen-containing wastewater, adds the nitric acid portion tail magnesium water containing nitrate radical, and adds USB reactor part and a small amount of dilution water recycling effluent dilutes waste water.In the water outlet of homogeneous equalizing tank, pH is 8.0, COD be 1964.0mg/L, TOC is 1189.2mg/L, and formic acid is 4970.0mg/L, and nitrate radical is 1053.3mg/L, and ammonia nitrogen concentration is 195.5mg/L.TOC/NO in waste water
3 --N ratio maintains about 5.0.
3rd step, adds urea concentration to 100mg/L in waste water, biphosphate potassium concn to 5mg/L(with PO
4 3-meter).
4th step, waste water gravity flow enters air flotation pool, removes suspended substance, colloid substances and cotton-shaped particulate matter in waste water further, and the oiliness foam produced in acid-base neutralisation process in early stage.
5th step, the waste water after precipitation-air-flotation enters USB reactor, and temperature of reaction is 36 DEG C.
6th step, USB water outlet enters aerobic reactor, and temperature of reaction is 36 DEG C.
The water quality situation of water outlet after denitrification-nitration treatment is as follows: pH is 7.7, COD be 78.56mg/L, TOC is 47.6mg/L, and formic acid content is less than 0.1mg/L, and ammonia-nitrogen content is less than 0.1mg/L, then COD Inlet and outlet water volumetric loading is 5.7kg/m
3d, TOC Inlet and outlet water volumetric loading is 3.4kg/m
3d, formic acid Inlet and outlet water volumetric loading is 14.9kg/m
3d, ammonia nitrogen Inlet and outlet water volumetric loading is 0.59kg/m
3d.
The content be not described in detail in this specification sheets belongs to the known prior art of professional and technical personnel in the field.
Claims (9)
1. the mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen, it is characterized in that, the described mutual-amido two polyaniline factory effluent containing ammonia nitrogen, for the mutual-amido two polyaniline factory effluent containing formic acid that produces in mutual-amido two polyaniline production process and the composite waste of Aniline Production waste water containing ammonia nitrogen, treatment step is as follows:
First pH regulator is carried out to the mutual-amido two polyaniline factory effluent containing formic acid, and then with containing the Aniline Production waste water mixing homogeneous of ammonia nitrogen, the waste water added in homogeneous equalizing tank containing nitrate radical completes the adjustment of C/N ratio to composite waste in homogeneous equalizing tank and pH value, and then N is added in homogeneous equalizing tank, P nutritive salt, if more containing waste residue amount in the water outlet of homogeneous equalizing tank, then need to carry out precipitation-air-flotation process to the water outlet of homogeneous equalizing tank, then high-enriched organics contained in the water outlet of homogeneous equalizing tank is removed by anti-nitration reaction, the basicity finally utilizing denitrification process to produce carries out the ammonia nitrogen in the water outlet of nitration reaction removal anti-nitration reaction, to realize discharged wastewater met the national standard,
Concrete treatment step is:
The first step, the mutual-amido two polyaniline factory effluent containing formic acid enters pH regulator pond, is adjusted to 4.5 ~ 6.0 with acid to its pH value;
Second step, the mutual-amido two polyaniline factory effluent containing formic acid of pH value has been regulated to enter homogeneous equalizing tank, with the Aniline Production waste water mixing homogeneous containing ammonia nitrogen in homogeneous equalizing tank, backward homogeneous equalizing tank in add nitrate solutions or provide the raw material required for denitrification containing the waste water of nitrate radical, and add and regulate composite waste pH value to 6.0 ~ 9.0 in homogeneous equalizing tank from the alkaline denitrification recirculation water of USB reactor and dilution water;
3rd step, adds N nutritive salt, P nutritive salt in homogeneous equalizing tank, to ensure that subsequent biochemical process is to N, P trace element demand;
4th step, if the waste residue amount contained in the water outlet of homogeneous equalizing tank is more, then the water outlet of homogeneous equalizing tank enters air flotation pool and carries out air supporting precipitation process, otherwise skips over this step;
5th step, delivers to USB reactor by the water outlet of homogeneous equalizing tank or the water outlet of air flotation pool and carries out anoxic denitrification reaction;
6th step, delivers to aerobic reactor by the water outlet of USB reactor and carries out aerobic nitrification reaction, and aerobic reactor water outlet COD is less than 80mg/L, and ammonia nitrogen is less than 15mg/L, reaches industrial wastewater discharge standard.
2. the mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen as claimed in claim 1, it is characterized in that, described containing formic acid and the water quality of composite waste containing ammonia nitrogen as follows: mutual-amido two polyaniline factory effluent pH is 10 ~ 13, COD is 50000 ~ 100000mg/L, TOC is 30000 ~ 60000mg/L, mainly contain organic pollutants in mutual-amido two polyaniline factory effluent to comprise: formic acid, aniline, phenol and p-nitrophenol, wherein said formic acid content is 114000 ~ 250000mg/L; In nitrogen-containing wastewater, ammonia nitrogen concentration is 200 ~ 350mg/L.
3. the mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen as claimed in claim 1, is characterized in that: acid described in the first step is HCl or HNO
3.
4. the mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen as claimed in claim 1, is characterized in that: by regulating the add-on of nitrate radical to make homogeneous equalizing tank TOC of yielding water/NO in second step
3 --N ratio is 2.0 ~ 5.0, occurs accumulation and ensure that denitrification process is to the demand of nitrate radical to prevent anti-nitration reaction Nitrite.
5. the mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen as claimed in claim 1, is characterized in that: the nitrate solutions described in second step is sodium nitrate solution, and the waste water containing nitrate radical described in second step is ammonium nitrate wastewater or nitric acid portion tail magnesium water.
6. the mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen as claimed in claim 1, is characterized in that: by composite waste pH value in the control of reflux ratio homogeneous equalizing tank of the alkaline denitrification recirculation water of adjustment in second step.
7. the mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen as claimed in claim 1, is characterized in that: described in the 3rd step, N nutritive salt is urea, adds in waste water and makes its concentration to 90 ~ 100mg/L; P nutritive salt is potassium primary phosphate, with PO
4 3-meter, adds in waste water and makes its concentration to 3 ~ 5mg/L.
8. the mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen as claimed in claim 1, is characterized in that: the controling parameters carrying out anoxic denitrification process described in the 5th step in USB reactor is as follows: COD Inlet and outlet water volumetric loading is 3.5 ~ 5.7kg/m
3d, TOC Inlet and outlet water volumetric loading is 2.0 ~ 3.5kg/m
3d, formic acid Inlet and outlet water volumetric loading is 8.0 ~ 16.0kg/m
3dissolved oxygen in d, USB reactor is less than 0.50mg/L, and anoxic denitrification temperature controls at 19 ~ 36 DEG C.
9. the mutual-amido two polyaniline production wastewater treatment method containing ammonia nitrogen as claimed in claim 1, is characterized in that: the temperature of reaction of the reaction of aerobic nitrification described in the 6th step controls at 22 ~ 36 DEG C, and in aerobic reactor, dissolved oxygen is greater than 2mg/L.
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