CN103112951A - Biochemical method for treating synthetic leather wastewater containing dimethylformamide - Google Patents
Biochemical method for treating synthetic leather wastewater containing dimethylformamide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
- C02F3/305—Nitrification and denitrification treatment characterised by the denitrification
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/301—Aerobic and anaerobic treatment in the same reactor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/38—Organic compounds containing nitrogen
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Abstract
The invention discloses a biochemical method for treating synthetic leather wastewater containing dimethylformamide and belongs to the field of wastewater treatment. The biochemical method comprises the following steps of: feeding the synthetic leather wastewater to be treated to a novel membrane bioreactor with an aerobic sludge-anaerobic packing structure, wherein the novel membrane bioreactor comprises an aerobic zone and an anaerobic zone; firstly enabling the synthetic leather wastewater to be treated to enter the aerobic zone in which specifically domesticated activated sludge with nitrifying bacteria as a dominant bacterial community is adopted, controlling the sludge return ratio of the aerobic zone to 100-300%, and adjusting the pH value of the aerobic zone to 8-9; enabling the synthetic leather wastewater treated in the aerobic zone to enter the anaerobic zone which is filled with a suspended filler and has a volumetric ratio of 30-60%; and discharging the synthetic leather wastewater treated in the anaerobic zone from the novel membrane bioreactor with the aerobic sludge-anaerobic packing structure. Through application of the biochemical method, the ammonia nitrogen and total nitrogen of outflow water can stably reach the Discharge Standard of Synthetic Leather and Artificial Leather Industrial Pollutants (GB21902-2008).
Description
Technical field
The present invention relates to synthetic leather and Tannery Wastewater Treatment Process field, more particularly, the present invention relates to the biochemical method that a kind of processing contains dimethyl formamide synthetic leather waste water.
Background technology
Synthetic leather waste water generally derives from following several strands of waste water: the water waste water of mixing, and between CODcr300 ~ 1500 mg/L, ammonia nitrogen is less than 50 mg/L; Washing trough water, between CODcr10000 ~ 20000 mg/L, this waste water enters recovery system; Wash tower waste water, between CODcr5000 ~ 20000 mg/L, ammonia nitrogen is less than 100 mg/L; Overhead water, as the products production water, so this type of waste water does not discharge substantially; The surface water and wash water, CODcr10000 ~ 20000 mg/L; Spraying water, very difficult, discontinuous discharging.
Use the DMF(dimethyl formamide in the surface treatment process of PU synthetic leather), DMF chemical formula (CH
3)
2NHCHO, stable chemical nature, and toxic the highlyest in China's surface water allows that the mass concentration recommendation is 25 mg/L.DMF on synthetic leather is produced only as organic solvent, do not participate in the chemical reaction process of leather-making technology, therefore, a large amount of DMF will mainly enter in synthetic leather waste water, and DMF will produce a large amount of ammonia nitrogens in the degradation processes such as biochemistry, compare traditional synthetic leather waste water, due to more to the inhibited composition of microorganism in synthetic leather waste water, ammonia nitrogen in synthetic leather waste water is more difficult effectively to be eliminated and degrades, therefore, in the synthetic leather wastewater treatment, Major Difficulties is effective degraded of DMF, even in the conventional indexs such as COD situation up to standard, in water outlet, also often fluctuation is very large for the ammonia nitrogen concentration level, be difficult to satisfy " synthetic leather and leatheroid emission of industrial pollutants standard " (GB21902-2008).
Ammonia nitrogen is one of main pollutant component in synthetic leather waste water, and the ammonia nitrogen discharge beyond standards that produces in present conventional Tannery Wastewater Treatment Technology often will cause serious Eutrophication Status, causes the lasting deterioration of ecotope.According to the monitoring of Keliang Bioengineering Co., Ltd., Hubei Prov., ionic state ammonia nitrogen toxicity a little less than, the NH of nonionic attitude
3-N toxicity is stronger, NH
3-N can enter the fish body by the gill membrane film, directly increase the burden that aquatic animal gets rid of useless nitrogen, often result causes the interior plurality of enzymes activity of aquatic organism to be suppressed, reduce the oxygen carrying capacity of blood, cause oxygen and waste exchange freely not to suffocate, therefore, the environmental quality that the various biologies of grievous injury are depended on for existence of the ammonia nitrogen in water body.
At present, effectively degrade for behavior of high-strength ammonium in trade effluent specially, the various technique means such as chemical precipitation method, blow-off method, ion exchange method, embrane method, catalytic oxidation, electrochemical process and ozone oxidation have been arranged.
The chemical precipitation fado adopts MgCl
26H
2O and Na
2HPO
412H
2O or MgO and H
3PO
4Make NH
4 +-N generates magnesium ammonium phosphate sediment, separates through gravitational settling or after filtering, thereby reaches the purpose of removing ammonia nitrogen." Chongqing Environmental Science " 2000,22 (6): 54 ~ 56 clock reasons, Zhan Huaiyu etc. " chemical precipitation method remove ammonia nitrogen in waste water and the discussion of reaction " thereof, studied the MAP method to the processing of slaughterhouse wastewater, leather-making waste water, waste water that the percolate ammonia-nitrogen content is high, although the MAP precipitator method have better treatment effect, but processing costs is higher, make use in leather-making waste water is processed uneconomical.
Blow-off method is except one of ammonia nitrogen common method in Practical Project, " the scientific and technological information exploitation is with economic " 1995,5 (1): 20 ~ 21 Wen Yan, Xiaoli Zhang, Cui Guifen: " blow-off method is removed the experimental study of ammonia nitrogen in waste water ", find that blow-off method is generally 30% ~ 50% to ammonia nitrogen removal frank, the extra high waste water clearance of nitrogen content can reach 90%, processing does not still reach emission request through stripping for containing the higher leather-making waste water of ammonia nitrogen amount, and working cost is high.
" Chinese leather " 2001,30(13): 23 ~ 27 Wen Zumou, Li Qing, heavy an ancient unit of weight: " research of tanning sewage treatment process technology ", studied with clorox and removed ammonia nitrogen in tanning sewage as oxygenant, ammonia nitrogen removal frank approximately 80%, the clorox consumption is with NaClO:NH
3Meter is about 6.5 ~ 8.0:1, this shows that oxidation style will reach comparatively ideal treatment effect, and it is large that the oxygenant consumption is wanted, and causes working cost higher, uneconomical as conventional processing.
Ion exchange method is to exchange by the positively charged ion on ion exchange resin and the ammonia nitrogen ion in waste water, and ion exchange resin material is zeolite commonly used, active zeolite generally." nonmetalliferous ore " 2009,32 (2), 68 ~ 71 fourths continue orchid, Li Ling, thunder minor benefit etc.: " natural zeolite and synthetic zeolite are removed the research of leather-making waste water ammonia-state nitrogen ", studies show that: zeolite has Adsorption preferably to the ammonia nitrogen in leather-making waste water, but the removal effect of the method easily is subjected to the impact of saltiness in waste water, and the ion-exchange fado is applied in the lower water treatment of ammonia-nitrogen content at present, recover the chemical processes such as regeneration because ion exchange resin generally all needs exchange capacity, the Industrial Wastewater Treatment that is directly used in high density is also more difficult.
In addition, also take absorption method, for example Chinese patent CN201840908U extraction is reclaimed, but operation is comparatively complicated.Microorganism is decomposed, for example Chinese patent CN101935626A, CN101914479A, but need the complex operations processes such as pure bacterium separation, enrichment and amplification.
Ammonia nitrogen in synthetic leather waste water is mainly derived from the DMF(dimethyl formamide) the biochemical degradation process, therefore, in synthetic leather waste water, the removal effect of nitrogen generally should comprise: the removal process of the degradation process of DMF and ammonia nitrogen two aspects.For processing and the recovery of DMF in waste water, there is following Patents to relate to.
The processing of a Chinese patent CN101074120 new organic waste water and the technology of resource utilization, the processing and the resource technology that particularly contain the organic waste water of the bio-refractory organic matters such as phenol, aniline, toluene, tetrahydrofuran (THF), hexalin, DMF, acetonitrile, methyl alcohol, ethanol, formic acid.To contain phenol, aniline, toluene, tetrahydrofuran (THF), hexalin, N, one or both in the organic matters such as dinethylformamide, acetonitrile, methyl alcohol, ethanol, formic acid or two or more organic waste water are raw material, under the Raney's nickel catalyst effect, under the temperature of 180 ~ 350 ℃ and 1 ~ 16MPa pressure, give birth to reforming reaction with steeping in water for reconstitution by the organic matter in waste water under catalyst action, generate hydrogen, methane, carbonic acid gas and carbon monoxide.But whole treating processes needs pressurization, adds gentle catalyst operation, and for the processing of organic waste water, the technological process operating parameters is harsh, and cost is higher.
Chinese patent CN101274169 chemical leather DMF waste liquor rectification reclaims pretreatment process, comprises the steps: that the DMF waste liquid that collects (1) squeezes into strainer via infusion pump and carry out flash trapping stage, and described strainer specification is: the 150-200 order; (2) the DMF waste liquid after flash trapping stage enters settling centrifuge and carries out the second-order separation, and the separation factor of described settling centrifuge is: 3000-11000; (3) above-mentioned I and II separates the solid slag that produces and burns or act as a fuel.This treating processes focus on pre-treatment to DMF impurity in removal process.
Chinese patent CN1982223 method for recovering synthetic-leather waste water, comprise the steps: that (1) at first filter pre-treatment, use microporous filtering method, except anhydrating middle fine suspension, as preprocessing means, protection main body reaction zone, pressure is 0.05 ~ 0.2MPa, effectively pore size filter is 5 ~ 10 μ m; (2) re-use catalyzer, at 80-95 ℃, the 10-20m/hr flow velocity under the 3-6/h air speed, carries out selective adsorption-catalyzed reaction and processes; (3) carry out at last secondary filter and process, its effective pore size filter 1 ~ 2 μ m.But whole treating processes needs temperature control, absorption and catalyst operation, and for the processing of organic waste water, the technological process operating parameters is harsh, and cost is higher.
Present existing processing PU synthetic leather waster water process mainly contains physico-chemical processes and the large class of biological process two, although stripping, precipitation, film absorb and the materialization such as wet oxidation to denitrogenate measure efficient higher, but usually just ammonia nitrogen has been carried out the phase transition of various ways, only transfer in atmosphere or solid phase from liquid phase, and bring corresponding environmental disposal cost and secondary pollution, and the ammonia nitrogen concentration of usually staying in mother liquor will be up between 20 ~ 100mg/L.Biological process can eliminate the organic pollutant in leather-making waste water effectively, have that the environmental facies dissolubility is high, running cost is low and simple operation and other advantages, but due to the restraining effect of Multiple components in leather-making waste water to nitrifying process, often cause the nitride in the biochemical process water outlet often to be difficult to realize qualified discharge.
For the effective main component such as the organism in degrading waste water and suspended substance of routine biochemistry art breading synthetic leather waste water, main water-quality guideline such as COD
Cr, BOD
5, SS etc. can accomplish qualified discharge, but unstable to the ammonia nitrogen in synthetic leather waste water and total nitrogen removal effect, the ammonia nitrogen concentration in water outlet is difficult to realize qualified discharge, becomes one of important factor that the further engineering of the conventional Tannery Wastewater Treatment Technology of restriction uses.Add the routine biochemistry reaction process for special physico-chemical pretreatment unit, can effectively degrade organism in synthetic leather waste water, the also effective ammonia nitrogen in degrading waste water simultaneously, cost of investment is high, technical process is long, technological operation is complicated and the running cost high, is difficult to obtain general promotion and application in the waste water treatment of the leather industry that comprises synthetic leather but exist.
Special in the DMF that contains in PU synthetic leather waste water, prior art has the multiple treatment technologies such as biological process, physico-chemical process (absorption, extraction), chemical method (catalyzed oxidation, supercritical water oxidation, alkaline hydrolysis).The physical chemistry methods such as extraction, absorption method are processed and are contained DMF waste water, compare biochemical process, and the materialization cell process is mainly used in containing the pre-treatment of DMF waste water.
Using traditional aerobic activated sludge process processing DMF waste water is a kind of economy, effective good method.Because DMF is biodegradable, can make sole carbon source and nitrogenous source comes culturing micro-organisms with DMF under aerobic condition; Microorganism respectively in aerobic, fermentation and nitrated environment, degraded DMF waste water under different concns, different pH condition, the DMF degradation rate is the highest under aerobic condition, product is NH
3Be added in active sludge with isolated microorganism or earth near the soil that often contacts trade effluent refinery, petrochemical plant device and go, enrichment, Isolation and screening are used for the bacterial classification of degraded DMF, as Pseudomonas minuscula and Pcrucivial, can realize obligate and efficient degradation to DMF contained in waste water.But in the process of the DMF nitrogenize of these biochemical methods in processing PU synthetic leather waste water, all there are the inevitable defectives such as culture condition is harsh, technical process is long, the Ammonia Nitrification degree is low.
Comprising at present the processing of the leather-making waste water of synthetic leather waste water, is that biological process and physico-chemical process are combined than conventional process, but the traditional biological processing is often undesirable to the ammonia nitrogen treatment effect mainly for high loading COD in waste water and other impurity." Jiangsu environmental science and technology " 1998,2: 11 ~ 13. benevolence are auspicious, and Yang Wei is magnificent: " air supporting-biochemistry-By Bubble-floating Method is processed synthetic leather waste water ", find due to Cr in leather-making waste water
3+, S
2-To the Ecotoxicology restraining effect, the concentration of ammonia nitrogen goes up not down Deng material." Environmental Pollution and Control " 2009; 31(3) 48 ~ 51; Deng Haihua, Shen Bin etc.: " the high ammonia nitrogen leather-making waste water research of the biological reinforced processing of ABFT "; process high ammonia-nitrogen wastewater by the biological reinforcing technology that adds the efficient denitrification microbiobacterial agent; process high ammonia nitrogen leather-making waste water and obtained treatment effect preferably; but this technique needs a large amount of high-efficiency strains, but the cultivation of characteristic high-efficiency strain needs higher production cost.But the Treatment of Tannery Wastewater with Biological Methods ammonia nitrogen is actual in engineering is the most feasible method, use biological process more economical and practical when especially the water yield is larger, so improve the traditional biological method, overcome the drawback of original biological process, researching and developing cost-effectively, biological removal of nitrogen technique is imperative.
Summary of the invention
The technical problem that invention will solve
The object of the invention is to overcome in prior art to containing the deficiency of dimethyl formamide synthetic leather wastewater treatment, provide a kind of processing to contain the biochemical method of dimethyl formamide synthetic leather waste water, the present invention integrated with strengthened the surface immobilized enrichment and growth of suspended packing fluidized bed microorganism and the membrane bioreactor biomass is high, mud-water separation efficient is high advantage, strengthened the effective degraded to DMF, making water outlet ammonia nitrogen qualified discharge, is a kind of economy, efficient biochemical processing method for containing DMF synthetic leather waste water.
Technical scheme
For achieving the above object, technical scheme provided by the invention is:
A kind of processing of the present invention contains the biochemical method of dimethyl formamide synthetic leather waste water, the steps include:
Step 1: with the pending new membrane bio-reactor that dimethyl formamide synthetic leather waste water passes into aerobic sludge-anaerobism filling-material structure that contains, control the influent quality index of synthetic leather waste water extremely: CODcr is 166-1276mg/L, ammonia nitrogen is 169-311mg/L, total nitrogen is 203-360mg/L, the new membrane bio-reactor of described aerobic sludge-anaerobism filling-material structure comprises aerobic zone and anaerobic zone, the design of the integrated or separated type of aerobic zone and anaerobic zone, the relative closures operation of twoth district;
step 2: the pending dimethyl formamide synthetic leather waste water that contains is introduced into aerobic zone, aerobic zone adopts the active sludge of obligate domestication take nitrifier as dominant microflora, acclimation period is 2-4 week, major nitrogen source is bicarbonate of ammonia, the compound of the various ways such as ammonium chloride, controlling the aerobic zone return sludge ratio is 100-300%, realize the complete denitrogenation of the various forms of nitride such as ammonia nitrogen, and the pH value of regulating aerobic zone is 8-9, the stirring of aerobic zone is provided by aeration tube, utilize aerobic activated sludge to realize nitration reaction, be nitrate nitrogen with mineralized nitrogen, and utilize separatory membrane to carry out mud-water separation, separatory membrane in the present invention adopts commercial microfiltration membrane or hyperfiltration membrane assembly,
Step 3: the synthetic leather waste water after processing through aerobic zone enters anaerobic zone, anaerobic zone is filled floating stuffing, volumetric ratio is between 30-60%, stirring power is provided by agitator, utilize immobilization anaerobe film to carry out anti-nitration reaction, the nitrate nitrogen that refluxes in the synthetic leather waste water of aerobic zone is converted into nitrogen;
Step 4: the synthetic leather waste water after processing through anaerobic zone is discharged the new membrane bio-reactor of aerobic sludge-anaerobism filling-material structure according to the order of sequence.
Preferably, the floating stuffing in step 3 is the polyethylene material, and outward appearance is the hollow round column body, and height is 7mm, and diameter is 10mm, and there is cross bracing inside, and there is fin the outside, and density is less than water, and voidage reaches 88%, and the total specific surface area of floating stuffing is 690 m
2/ m
3, the effective ratio area that adheres to for microbial film is 500m
2/ m
3
Preferably, pass in step 1 pending contain dimethyl formamide synthetic leather waste water before, the vexed phase of exposing to the sun at initial stage of the new membrane bio-reactor of aerobic sludge-anaerobism filling-material structure is 5 days, intermittently changes water, the COD load is 0.6kg/m
3D, ammonia nitrogen loading are 0.2kg/m
3D, the total nitrogen load is 0.3kg/m
3D after 10 days, improves 5% influent load every day, moves steady running after 3 months.
Contain the DMF(dimethyl formamide in synthetic leather waste water), the DMF nitrogen content is high, one of biochemical degradation process product is exactly ammonia nitrogen, main improvement of the present invention is fully based on ammonia nitrogen aerobic nitrification, anaerobic denitrification biological degradation principle, the new membrane bio-reactor of aerobic sludge reasonable in design-anaerobism filling-material structure, take full advantage of commercial microfiltration membrane or the hyperfiltration membrane assembly crown_interception good to microorganisms such as nitrifiers, realize the efficient removal of ammonia nitrogen and total nitrogen in PU synthetic leather waste water, realize the qualified discharge of synthetic leather waste water.Specifically, the anaerobic part that the present invention includes is realized nitrogenize and denitrification to DMF; Aerobic part, the main realization transforms by DMF the nitrification that produces ammonia nitrogen, and floating stuffing and separatory membrane are the strengthening effects that realizes whole biological process.The new membrane bio-reactor of aerobic sludge in the present invention-anaerobism filling-material structure is made of aerobic zone and anaerobic zone Two-Stage Biochemical reaction member, integrated membrane bioreactor and the technical superiority of suspended packing fluidized bed in high strength industrial waste water.Wherein aerobic zone utilizes aerobic activated sludge to realize nitration reaction, is nitrate nitrogen with mineralized nitrogen, and utilizes the mud-water separation function of separatory membrane film to realize the water outlet of low-concentration ammonia-nitrogen, low suspended substance and colourity; Anaerobic zone utilizes immobilization anaerobe film to carry out anti-nitration reaction, the nitride that refluxes in the waste water of aerobic zone is converted into nitrogen, synthetic leather waste water is through the processing of the new membrane bio-reactor of aerobic sludge-anaerobism filling-material structure, when realizing the organism steady removal, also can realize the qualified discharge of the nitride such as ammonia nitrogen, and embody that running cost is low, compact construction, level of automation advantages of higher.
Beneficial effect
Adopt technical scheme provided by the invention, compare with existing known technology, have following unusual effect:
(1) a kind of processing of the present invention contains the biochemical method of dimethyl formamide synthetic leather waste water, due to the new membrane bio-reactor that adopts aerobic sludge-anaerobism filling-material structure, the organism qualified discharge simultaneously in realizing waste water, can effectively degrade ammonia nitrogen in synthetic leather waste water, realize the qualified discharge of ammonia nitrogen, ammonia nitrogen removal frank reaches 95% left and right, go out below water concentration 8mg/L, the clearance of total nitrogen reaches 90% left and right, the total nitrogen concentration of water outlet is stabilized in below 15mg/L, water outlet ammonia nitrogen and total nitrogen can be stablized and reach " synthetic leather and leatheroid emission of industrial pollutants standard " (GB21902-2008) Ammonia-nitrogen From Leather Making Wastewater, the emission standard of total nitrogen, the synthetic leather waste strength is processed in experiment: CODcr 166-1276mg/L, ammonia nitrogen 169-311mg/L, total nitrogen 203-360mg/L, water outlet can be stabilized in: CODcr 39-58mg/L, ammonia nitrogen 4.2-7.4mg/L, total nitrogen 8.5-13.8mg/L,
(2) a kind of processing of the present invention biochemical method of containing dimethyl formamide synthetic leather waste water is compared the characteristics of A/O technique: conventional A/O technique is cascaded leading portion anoxic section and back segment aerobic section, and A section DO is not more than 0.2mg/L, O section DO=2 ~ 4mg/L.Anoxic section heterotrophic bacterium, the suspended contaminant such as the starch in sewage, fiber, carbohydrate and dissolved organic matter are hydrolyzed to organic acid, make larger molecular organics be decomposed into small organic molecule, heterotrophic bacterium carries out ammonification with pollutents such as protein, fat, and ammonia (NH dissociates
3, NH
4 +); In the nitrification of aerobic section autotrophic bacteria with NH
3-N(NH
4 +) be oxidized to HO
3 -, control by backflow and be back to the A pond, under anoxia condition, the denitrification of heterotrophic bacteria is with NO
3 -Be reduced to molecular nitrogen (N
2) complete C, N, the O circulation in ecology, realize the sewage harmless treatment, A/O technique has been the technique of commonplace employing in general city or industrial sewage at present.But adopt A/O technique to have certain limitation: the process control of A/O process operation easily produces sludge bulking and loss, and Nitrogen/Phosphorus Removal is relatively poor.MLSS generally should be more than 3000mg/L, obviously reduces lower than this value A/O system denitrification effect.The TN/MLSS rate of load condensate should be under 0.05gTN/ (gMLSSd) in nitration reaction, is worth higher than this that nitrification effect is relatively poor.In nitration reaction, affecting nitrated principal element is existence and the activity of nitrifier, because be 0.21/d from oxygen type nitrifier minimum than rate of growth; And the minimum specific growth rate of heterotroph aerobic bacteria is 1.2/d.Nitrifier survived and preponderate, requiring sludge age greater than 4.76d; So nitrifier can not take advantage in active sludge, when ammonia nitrogen concentration was higher, nitrification effect was very poor;
And aerobic zone of the present invention can all be trapped in all microorganisms in reactor, for the low microorganism of Specific incremental rate, (as nitrifier) has good concentration effect, therefore, the ammonia nitrogen of higher concentration in sewage had good removal effect, in addition, because separatory membrane (microfiltration membrane or ultra-filtration membrane) can all be trapped in reactor all mud, therefore, have higher biomass in reactor, therefore have the removal potentiality higher to waste water.Anaerobic zone utilizes immobilization anaerobe film to carry out anti-nitration reaction, the nitride that refluxes in the waste water of aerobic zone is converted into nitrogen, waste water is through the processing of the new membrane bio-reactor of anaerobic-aerobic distribution, when realizing the organism steady removal, also can realize the qualified discharge of the nitride such as ammonia nitrogen.With respect to traditional A/O technique, embody, anti-shock loading high to organic matter degradation efficient large, be difficult for that sludge bulking, efficiencies of nitrogen removal are good, compact construction and level of automation advantages of higher.
Description of drawings
Fig. 1 is that a kind of processing of the present invention contains the biochemical method of dimethyl formamide synthetic leather waste water to the removal effect of COD;
Fig. 2 is that a kind of processing of the present invention contains the biochemical method of dimethyl formamide synthetic leather waste water to the removal effect of total nitrogen;
Fig. 3 is that a kind of processing of the present invention contains the biochemical method of dimethyl formamide synthetic leather waste water to the removal effect of ammonia nitrogen;
Fig. 4 is the structural representation of the new membrane bio-reactor of aerobic sludge in the present invention-anaerobism filling-material structure;
Fig. 5 is the A-A sectional view in Fig. 4;
Fig. 6 is the B-B sectional view in Fig. 4.
Label declaration in schematic diagram is as follows: 1, water inlet pipe; 2, aeration tube; 3, separatory membrane; 4, membrane support; 5, aerobic zone; 6, anaerobic zone; 7, agitator.
Embodiment
For further understanding content of the present invention, the present invention is described in detail in conjunction with the accompanying drawings and embodiments.
Certain synthetic leather process hides company, produce the Large-scale enterprises of 24 myriametre PU leather per year, approximately 80,000 ton/years of wastewater discharges, its waste water feature leather industry at home has suitable representativeness, original process is hydrolysis+catalytic oxidation+coagulating sedimentation, effluent index is ammonia nitrogen 150-180mg/L, and wherein ammonia nitrogen exceeds standard seriously.But use biochemical method of the present invention, but comprise the equal qualified discharge of pollutent index of total nitrogen, ammonia nitrogen, concrete treatment step is:
Step 1: with the pending new membrane bio-reactor that dimethyl formamide synthetic leather waste water passes into aerobic sludge-anaerobism filling-material structure that contains, control the influent quality index of synthetic leather waste water extremely: CODcr is 166-1276mg/L, ammonia nitrogen is 169-311mg/L, total nitrogen is that 203-360mg/L all can, in the present embodiment, the influent quality index is as shown in table 1, the new membrane bio-reactor of this aerobic sludge-anaerobism filling-material structure comprises aerobic zone 5 and anaerobic zone 6, the design of the integrated or separated type of aerobic zone 5 and anaerobic zone 6, the relative closures operation of twoth district.Specifically in conjunction with Fig. 4, Fig. 5 and shown in Figure 6, the new membrane bio-reactor of the aerobic sludge in the present invention-anaerobism filling-material structure comprises: water inlet pipe 1, aeration tube 2, separatory membrane 3, membrane support 4, aerobic zone 5, anaerobic zone 6 and agitator 7, this new membrane bio-reactor main body comprises aerobic zone 5 and anaerobic zone 6, separatory membrane 3 is fixed in aerobic zone 5 by membrane support 4, agitator 7 is fixedly mounted in anaerobic zone 6, carries out aeration by aeration tube 2 in aerobic zone 5.In the present embodiment pass into pending contain dimethyl formamide synthetic leather waste water before, the vexed phase of exposing to the sun at initial stage of the new membrane bio-reactor of aerobic sludge-anaerobism filling-material structure is 5 days, intermittently changes water, the COD load is 0.6kg/m
3D, ammonia nitrogen loading are 0.2kg/m
3D, the total nitrogen load is 0.3kg/m
3D after 10 days, improves 5% influent load every day, moves steady running after 3 months.
step 2: the pending dimethyl formamide synthetic leather waste water that contains is introduced into aerobic zone 5, aerobic zone 5 adopts the active sludge of obligate domestication take nitrifier as dominant microflora, acclimation period was 3 weeks, major nitrogen source is bicarbonate of ammonia, the compound of the various ways such as ammonium chloride, controlling aerobic zone 5 return sludge ratios is 200%, realize the complete denitrogenation of the various forms of nitride such as ammonia nitrogen, and the pH value of regulating aerobic zone 5 is 8.5, the stirring of aerobic zone 5 is provided by aeration tube 2, utilize aerobic activated sludge to realize nitration reaction, be nitrate nitrogen with mineralized nitrogen, and utilize separatory membrane 3 to carry out mud-water separation, separatory membrane 3 in the present invention adopts commercial microfiltration membrane or hyperfiltration membrane assembly.
Step 3: the synthetic leather waste water after processing through aerobic zone 5 enters anaerobic zone 6, anaerobic zone 6 is filled floating stuffing, and volumetric ratio is between 45%, and the floating stuffing in the present embodiment is the polyethylene material, outward appearance is the hollow round column body, height is 7mm, and diameter is 10mm, and there is cross bracing inside, there is fin the outside, density is less than water, and voidage reaches 88%, and the total specific surface area of floating stuffing is 690 m
2/ m
3, the effective ratio area that adheres to for microbial film is 500m
2/ m
3, stirring power is provided by agitator 7, utilizes immobilization anaerobe film to carry out anti-nitration reaction, and the nitrate nitrogen that refluxes in the synthetic leather waste water of aerobic zone 5 is converted into nitrogen.
Step 4: the synthetic leather waste water after processing through anaerobic zone 6 is discharged the new membrane bio-reactor of aerobic sludge-anaerobism filling-material structure according to the order of sequence, and water-quality guideline changes as shown in the table.
The water-quality guideline mean change situation of table 1 embodiment 1
| The principal pollutant index | Influent concentration (mg/L) | Go out water concentration (mg/L) | Clearance (%) |
| CODcr | 468.3 | 40 | 91.46 |
| NH 4 +-N | 201.1 | 8 | 96.02 |
| N | 275.7 | 15 | 94.56 |
Certain synthetic leather process hides company, approximately 50,000 ton/years of wastewater discharges, its ammonia nitrogen in waste water throughout the year can not stably reaching standards, and wherein ammonia nitrogen exceeds standard seriously.Use biochemical method of the present invention, but comprise the equal qualified discharge of pollutent index of total nitrogen, ammonia nitrogen, concrete treatment step is:
Step 1: with the pending new membrane bio-reactor that dimethyl formamide synthetic leather waste water passes into aerobic sludge-anaerobism filling-material structure that contains, control the influent quality index of synthetic leather waste water extremely: CODcr is 166-1276mg/L, ammonia nitrogen is 169-311mg/L, total nitrogen is that 203-360mg/L all can, in the present embodiment, the influent quality index is as shown in table 2, the new membrane bio-reactor of this aerobic sludge-anaerobism filling-material structure comprises aerobic zone 5 and anaerobic zone 6, the design of the integrated or separated type of aerobic zone 5 and anaerobic zone 6, the relative closures operation of twoth district.Specifically in conjunction with Fig. 4, Fig. 5 and shown in Figure 6, the new membrane bio-reactor of the aerobic sludge in the present invention-anaerobism filling-material structure comprises: water inlet pipe 1, aeration tube 2, separatory membrane 3, membrane support 4, aerobic zone 5, anaerobic zone 6 and agitator 7, this new membrane bio-reactor main body comprises aerobic zone 5 and anaerobic zone 6, separatory membrane 3 is fixed in aerobic zone 5 by membrane support 4, agitator 7 is fixedly mounted in anaerobic zone 6, carries out aeration by aeration tube 2 in aerobic zone 5.In the present embodiment pass into pending contain dimethyl formamide synthetic leather waste water before, the vexed phase of exposing to the sun at initial stage of the new membrane bio-reactor of aerobic sludge-anaerobism filling-material structure is 5 days, intermittently changes water, the COD load is 0.6kg/m
3D, ammonia nitrogen loading are 0.2kg/m
3D, the total nitrogen load is 0.3kg/m
3D after 10 days, improves 5% influent load every day, moves steady running after 3 months.
step 2: the pending dimethyl formamide synthetic leather waste water that contains is introduced into aerobic zone 5, aerobic zone 5 adopts the active sludge of obligate domestication take nitrifier as dominant microflora, active sludge is from the aeration tank mud of Hangzhou synthetic leather waste water, acclimation period was 2 weeks, major nitrogen source is bicarbonate of ammonia, the compound of the various ways such as ammonium chloride, controlling aerobic zone 5 return sludge ratios is 100%, realize the complete denitrogenation of the various forms of nitride such as ammonia nitrogen, and the pH value of regulating aerobic zone 5 is 8, the stirring of aerobic zone 5 is provided by aeration tube 2, utilize aerobic activated sludge to realize nitration reaction, be nitrate nitrogen with mineralized nitrogen, and utilize separatory membrane 3 to carry out mud-water separation, separatory membrane 3 in the present invention adopts commercial microfiltration membrane or hyperfiltration membrane assembly.
Step 3: the synthetic leather waste water after processing through aerobic zone 5 enters anaerobic zone 6, anaerobic zone 6 is filled floating stuffing, and volumetric ratio is between 30%, and the floating stuffing in the present embodiment is the polyethylene material, outward appearance is the hollow round column body, height is 7mm, and diameter is 10mm, and there is cross bracing inside, there is fin the outside, density is less than water, and voidage reaches 88%, and the total specific surface area of floating stuffing is 690 m
2/ m
3, the effective ratio area that adheres to for microbial film is 500m
2/ m
3, stirring power is provided by agitator 7, utilizes immobilization anaerobe film to carry out anti-nitration reaction, and the nitrate nitrogen that refluxes in the synthetic leather waste water of aerobic zone 5 is converted into nitrogen.
Step 4: the synthetic leather waste water after processing through anaerobic zone 6 is discharged the new membrane bio-reactor of aerobic sludge-anaerobism filling-material structure according to the order of sequence, and water-quality guideline changes as shown in the table.
The water-quality guideline changing conditions of table 2 embodiment 2
| The principal pollutant index | Influent concentration (mg/L) | Go out water concentration (mg/L) | Clearance (%) |
| CODcr | 359.4 | 25 | 93.04 |
| NH 4 +-N | 187.2 | 7.3 | 96.1 |
| N | 232.6 | 12 | 94.84 |
Certain synthetic leather process hides company, approximately 50,000 ton/years of wastewater discharges, its ammonia nitrogen in waste water throughout the year can not stably reaching standards, and wherein ammonia nitrogen exceeds standard seriously.Use biochemical method of the present invention, but comprise the equal qualified discharge of pollutent index of total nitrogen, ammonia nitrogen, concrete treatment step is:
Step 1: with the pending new membrane bio-reactor that dimethyl formamide synthetic leather waste water passes into aerobic sludge-anaerobism filling-material structure that contains, control the influent quality index of synthetic leather waste water extremely: CODcr is 166-1276mg/L, ammonia nitrogen is 169-311mg/L, total nitrogen is that 203-360mg/L all can, in the present embodiment, the influent quality index is as shown in table 3, the new membrane bio-reactor of this aerobic sludge-anaerobism filling-material structure comprises aerobic zone 5 and anaerobic zone 6, the design of the integrated or separated type of aerobic zone 5 and anaerobic zone 6, the relative closures operation of twoth district.Specifically in conjunction with Fig. 4, Fig. 5 and shown in Figure 6, the new membrane bio-reactor of the aerobic sludge in the present invention-anaerobism filling-material structure comprises: water inlet pipe 1, aeration tube 2, separatory membrane 3, membrane support 4, aerobic zone 5, anaerobic zone 6 and agitator 7, this new membrane bio-reactor main body comprises aerobic zone 5 and anaerobic zone 6, separatory membrane 3 is fixed in aerobic zone 5 by membrane support 4, agitator 7 is fixedly mounted in anaerobic zone 6, carries out aeration by aeration tube 2 in aerobic zone 5.In the present embodiment pass into pending contain dimethyl formamide synthetic leather waste water before, the vexed phase of exposing to the sun at initial stage of the new membrane bio-reactor of aerobic sludge-anaerobism filling-material structure is 5 days, intermittently changes water, the COD load is 0.6kg/m
3D, ammonia nitrogen loading are 0.2kg/m
3D, the total nitrogen load is 0.3kg/m
3D after 10 days, improves 5% influent load every day, moves steady running after 3 months.
step 2: the pending dimethyl formamide synthetic leather waste water that contains is introduced into aerobic zone 5, aerobic zone 5 adopts the active sludge of obligate domestication take nitrifier as dominant microflora, acclimation period was 4 weeks, major nitrogen source is bicarbonate of ammonia, the compound of the various ways such as ammonium chloride, controlling aerobic zone 5 return sludge ratios is 300%, realize the complete denitrogenation of the various forms of nitride such as ammonia nitrogen, and the pH value of regulating aerobic zone 5 is 9, the stirring of aerobic zone 5 is provided by aeration tube 2, utilize aerobic activated sludge to realize nitration reaction, be nitrate nitrogen with mineralized nitrogen, and utilize separatory membrane 3 to carry out mud-water separation, separatory membrane 3 in the present invention adopts commercial microfiltration membrane or hyperfiltration membrane assembly.
Step 3: the synthetic leather waste water after processing through aerobic zone 5 enters anaerobic zone 6, anaerobic zone 6 is filled floating stuffing, and volumetric ratio is between 60%, and the floating stuffing in the present embodiment is the polyethylene material, outward appearance is the hollow round column body, height is 7mm, and diameter is 10mm, and there is cross bracing inside, there is fin the outside, density is less than water, and voidage reaches 88%, and the total specific surface area of floating stuffing is 690 m
2/ m
3, the effective ratio area that adheres to for microbial film is 500m
2/ m
3, stirring power is provided by agitator 7, utilizes immobilization anaerobe film to carry out anti-nitration reaction, and the nitrate nitrogen that refluxes in the synthetic leather waste water of aerobic zone 5 is converted into nitrogen.
Step 4: the synthetic leather waste water after processing through anaerobic zone 6 is discharged the new membrane bio-reactor of aerobic sludge-anaerobism filling-material structure according to the order of sequence, and water-quality guideline changes as shown in the table.
The water-quality guideline changing conditions of table 3 embodiment 3
| The principal pollutant index | Influent concentration (mg/L) | Go out water concentration (mg/L) | Clearance (%) |
| CODcr | 852.6 | 57.3 | 93.28 |
| NH 4 +-N | 309.6 | 7.1 | 97.71 |
| N | 275.7 | 14 | 94.92 |
A kind of processing of the present invention contains the biochemical method of dimethyl formamide synthetic leather waste water, its main technological merit can be concentrated and be: use the present invention, except can normally removing the index such as organism, can make total nitrogen and stable " synthetic leather and leatheroid emission of industrial pollutants standard " (GB21902-2008) emission standard of Ammonia-nitrogen From Leather Making Wastewater, total nitrogen that reaches of ammonia nitrogen of the synthetic leather waste water that contains DMF.
Illustrate that below in conjunction with typical test running condition method of the present invention is to containing the treatment effect of dimethyl formamide synthetic leather waste water.Carry out the test run(s) of continuous 3 wheat harvesting periods for the aerobic sludge in certain process hides Sewage Plant employing the present invention of the company-new membrane bio-reactor of anaerobism filling-material structure, test shows that this new membrane bio-reactor is remarkable to the synthetic leather water treatment effect, and total nitrogen especially wherein and ammonia nitrogen treatment effect are more stable.
Fig. 1 is that the present invention is to the removal effect of COD, as can be seen from Figure 1: the unloading phase (that is: stage 1) debugging influent COD be down to 210.9mg/L from 1276.2mg/L, water outlet COD is between 100mg/L to 158mg/L, although water outlet COD is greater than 100mg/L, but the unloading phase, the COD clearance is on a declining curve generally, average removal rate only 64.3%.Stable operation stage (that is: stage 2) (33d～105d), influent COD on average maintains 358.8mg/L, and water outlet COD average out to 45.5mg/L, the clearance average out to 72.4% of method of the present invention to COD, water outlet COD is substantially lower than 50mg/L.
Fig. 2 be the present invention to the removal effect of total nitrogen, although the fluctuation of concentration of water inlet total nitrogen is larger, total water outlet total nitrogen concentration is always in steady decrease, the present invention also continues to be increased to more than 90% to the clearance of total nitrogen thereupon.The concentration level of water outlet total nitrogen is stable lower than 10mg/L, has reached the emission standard of leather-making waste water to total nitrogen.
Fig. 3 be the present invention to the removal effect of ammonia nitrogen, can learn method of the present invention to the ammonia nitrogen removal successful by Fig. 3, stable after the water outlet ammonia nitrogen lower than 15mg/L.
Claims (3)
1. a processing contains the biochemical method of dimethyl formamide synthetic leather waste water, the steps include:
Step 1: with the pending new membrane bio-reactor that dimethyl formamide synthetic leather waste water passes into aerobic sludge-anaerobism filling-material structure that contains, control the influent quality index of synthetic leather waste water extremely: CODcr is 166-1276mg/L, ammonia nitrogen is 169-311mg/L, total nitrogen is 203-360mg/L, the new membrane bio-reactor of described aerobic sludge-anaerobism filling-material structure comprises aerobic zone and anaerobic zone, the design of the integrated or separated type of aerobic zone and anaerobic zone, the relative closures operation of twoth district;
Step 2: the pending dimethyl formamide synthetic leather waste water that contains is introduced into aerobic zone, aerobic zone adopts the active sludge of obligate domestication take nitrifier as dominant microflora, acclimation period is 2-4 week, controlling the aerobic zone return sludge ratio is 100-300%, and the pH value of regulating aerobic zone is 8-9, and the stirring of aerobic zone is provided by aeration tube, utilizes aerobic activated sludge to realize nitration reaction, be nitrate nitrogen with mineralized nitrogen, and utilize separatory membrane to carry out mud-water separation;
Step 3: the synthetic leather waste water after processing through aerobic zone enters anaerobic zone, anaerobic zone is filled floating stuffing, volumetric ratio is between 30-60%, stirring power is provided by agitator, utilize immobilization anaerobe film to carry out anti-nitration reaction, the nitrate nitrogen that refluxes in the synthetic leather waste water of aerobic zone is converted into nitrogen;
Step 4: the synthetic leather waste water after processing through anaerobic zone is discharged the new membrane bio-reactor of aerobic sludge-anaerobism filling-material structure according to the order of sequence.
2. a kind of processing according to claim 1 contains the biochemical method of dimethyl formamide synthetic leather waste water, it is characterized in that: the floating stuffing in step 3 is the polyethylene material, outward appearance is the hollow round column body, height is 7mm, and diameter is 10mm, and there is cross bracing inside, there is fin the outside, density is less than water, and voidage reaches 88%, and the total specific surface area of floating stuffing is 690 m
2/ m
3, the effective ratio area that adheres to for microbial film is 500m
2/ m
3
3. a kind of processing according to claim 2 contains the biochemical method of dimethyl formamide synthetic leather waste water, it is characterized in that: pass in step 1 pending contain dimethyl formamide synthetic leather waste water before, the vexed phase of exposing to the sun at initial stage of the new membrane bio-reactor of aerobic sludge-anaerobism filling-material structure is 5 days, intermittently change water, the COD load is 0.6kg/m
3D, ammonia nitrogen loading are 0.2kg/m
3D, the total nitrogen load is 0.3kg/m
3D after 10 days, improves 5% influent load every day, moves steady running after 3 months.
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| PCT/CN2013/087189 WO2014146439A1 (en) | 2013-03-18 | 2013-11-15 | Biochemical method for treating synthetic leather wastewater comprising dimethylformamide |
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| WO2014146439A1 (en) * | 2013-03-18 | 2014-09-25 | 南京大学宜兴环保研究院 | Biochemical method for treating synthetic leather wastewater comprising dimethylformamide |
| CN105198174A (en) * | 2015-10-29 | 2015-12-30 | 南京大学盐城环保技术与工程研究院 | Method for treating chemical industry wastewater containing organic nitrogen DMF (N,N-dimethylformamide) |
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