WO2014146439A1 - 一种处理含二甲基甲酰胺合成革废水的生化方法 - Google Patents

一种处理含二甲基甲酰胺合成革废水的生化方法 Download PDF

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WO2014146439A1
WO2014146439A1 PCT/CN2013/087189 CN2013087189W WO2014146439A1 WO 2014146439 A1 WO2014146439 A1 WO 2014146439A1 CN 2013087189 W CN2013087189 W CN 2013087189W WO 2014146439 A1 WO2014146439 A1 WO 2014146439A1
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synthetic leather
aerobic
wastewater
zone
anaerobic
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PCT/CN2013/087189
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English (en)
French (fr)
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王庆
丁原红
任洪强
王艳茹
任鑫坤
刘敏敏
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南京大学宜兴环保研究院
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Publication of WO2014146439A1 publication Critical patent/WO2014146439A1/zh

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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
    • 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
    • C02F3/301—Aerobic and anaerobic treatment in the same reactor
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

Definitions

  • the present invention relates to the field of synthetic leather and tannery wastewater treatment technology, and more particularly to a biochemical process for treating wastewater containing dimethylformamide synthetic leather.
  • Synthetic leather wastewater is generally derived from the following wastewaters: leeches, CODcr between 300 and 1500 mg/L, ammonia nitrogen less than 50 mg/L; washing water, CODcrl 0000 ⁇ 20000 mg/L, this wastewater enters Recovery system; Washing tower wastewater, between CODcr 5000 ⁇ 20000 mg/L, ammonia nitrogen less than 100 mg/L; Top water, as product production water, so this kind of wastewater is basically not discharged; Ground water and washing water, CODcrl0000 ⁇ 20000 Mg/L; spray water, very difficult to handle, non-continuous discharge.
  • the surface treatment of PU synthetic leather uses DMF (dimethylformamide), DMF chemical formula (CH 3 ) 2 NHCHO, chemically stable, and toxic.
  • DMF dimethylformamide
  • CH 3 DMF chemical formula
  • the recommended maximum concentration of surface water in China is 25 mg. /L.
  • DMF is only used as an organic solvent in the production of synthetic leather. It does not participate in the chemical reaction process of the tanning process. Therefore, a large amount of DMF will mainly enter the synthetic leather wastewater, and DMF will produce a large amount of ammonia nitrogen in the biochemical degradation process.
  • the traditional synthetic leather wastewater because the synthetic leather wastewater has more inhibitory effects on microorganisms, the ammonia nitrogen in the synthetic leather wastewater is more difficult to effectively remove and degrade.
  • the main difficulty in the treatment of synthetic leather wastewater is the effective degradation of DMF, even Under the condition that the conventional indicators such as COD meet the standards, the ammonia nitrogen concentration level in the effluent also tends to fluctuate greatly, and it is difficult to meet the “Emission Standards for Pollutants of Synthetic Leather and Artificial Leather Industry” (GB21902-2008).
  • Ammonia nitrogen is one of the main pollutants in synthetic leather wastewater.
  • the excessive emission of ammonia nitrogen generated in the conventional tannery wastewater treatment process will often lead to serious eutrophication of water bodies, causing continuous deterioration of the ecological environment.
  • the ionic ammonia nitrogen is weak, and the non-ionic NH 3 -N is more toxic.
  • NH 3 -N will enter the fish through the sputum membrane, directly increasing the aquatic animal to eliminate waste.
  • the burden of nitrogen often results in inhibition of various enzyme activities in aquatic organisms, lowering the oxygen transport capacity of the blood, resulting in poor exchange of oxygen and waste. Therefore, the ammonia nitrogen in the water will seriously damage the environment in which various organisms depend. quality.
  • the chemical precipitation method mostly uses MgCl 2 ⁇ 6H 2 0 and ⁇ Na 2 HP 0 4 ⁇ 12H 2 0 or MgO and H 3 P0 4 to make NH 4 + -
  • N produces magnesium ammonium phosphate precipitate, which is precipitated by gravity or filtered and separated to achieve the purpose of removing ammonia nitrogen.
  • the MAP method was applied to the treatment of wastewater with high ammonia nitrogen content in slaughter wastewater, tannery wastewater and landfill leachate. Although the MAP precipitation method has a good treatment effect, the treatment cost is high, which makes the application in tannery wastewater treatment uneconomical.
  • the blow-off method is one of the common methods for removing ammonia nitrogen in practical engineering. Science and Technology Information Development and Economy 1995,5 (1) : 20-21 Wen Wei, Zhang Xiaoli, Cui Guifen: Experimental Study on Removal of Ammonia Nitrogen from Wastewater by Stripping Method ", it is found that the removal rate of ammonia nitrogen is generally 30% to 50%, and the removal rate of wastewater with particularly high nitrogen content can reach 90%. For the tannery wastewater with higher ammonia nitrogen content, it is still not discharged after being stripped. Requirements, and running costs are expensive.
  • the ion exchange method is carried out by exchange of cations on the ionic resin with ammonia nitrogen ions in the wastewater.
  • the ion exchange resin materials are generally zeolites and activated zeolites.
  • the ammonia nitrogen in the process has better adsorption and removal, but the removal effect of the method is easily affected by the salt content in the wastewater.
  • the ion exchange method is mostly applied to water treatment with low ammonia nitrogen content, because ion exchange resins are generally required.
  • the exchange capacity restores chemical processes such as regeneration, and it is still difficult to directly use it for high-concentration industrial wastewater treatment.
  • the ammonia nitrogen in the synthetic leather wastewater is mainly derived from the biodegradation process of DMF (dimethylformamide). Therefore, the removal effect of nitrogen in the synthetic leather wastewater generally includes: DMF degradation process and ammonia nitrogen removal process. aspect.
  • DMF dimethylformamide
  • Chinese patent CN101074120 - a new technology for the treatment and recycling of organic wastewater, especially containing phenol, aniline, toluene, tetrahydrofuran, cyclohexanol, N, N-dimethylformamide, acetonitrile, methanol, ethanol
  • treatment and resource technology of organic wastewater that is difficult to degrade organic matter such as formic acid. Taking one or two or more organic waste waters containing phenol, aniline, toluene, tetrahydrofuran, cyclohexanol, N, N-dimethylformamide, acetonitrile, methanol, ethanol, formic acid, etc.
  • the separation factor of the sedimentation centrifuge is: 3000-11000; (3) The above-mentioned first and second separation The solid waste produced is incinerated or used as a fuel. The focus of this process is on the pretreatment of DMF impurities during the recovery process.
  • Chinese patent CN1982223 synthetic leather wastewater reuse method comprising the following steps: (1) First, the filtration pretreatment is performed, and the microporous filtration method is used to remove the fine suspended matter in the water as a pretreatment means to protect the main reaction zone, and the pressure is 0.05 ⁇ 0.2MPa, effective filtration pore size is 5 ⁇ 10 ⁇ m; (2) Re-use catalyst, selective adsorption at 80-95 °C, 10-20m/hr flow rate, 3-6/h space velocity Catalytic reaction treatment; (3) Finally, the precision filtration treatment is carried out, and the effective filtration pore size is 1 ⁇ 2 ⁇ ⁇ . However, the whole process requires temperature control, adsorption and catalytic operation. For the treatment of organic wastewater, the process parameters are harsh and costly.
  • the existing processes for treating PU synthetic leather wastewater mainly include physical chemical method and biological method.
  • the physical nitrogen removal measures such as stripping, sedimentation, membrane absorption and wet oxidation are more efficient, they are usually only for ammonia nitrogen.
  • Various forms of phase transfer have been carried out, only from the liquid phase to the atmosphere or solid phase, and bring the corresponding environmental disposal costs and secondary pollution, and the ammonia nitrogen concentration usually left in the mother liquor will still be as high as 20 ⁇ 100mg.
  • the biochemical process can effectively remove the organic pollutants in the tannery wastewater, and has the advantages of high environmental compatibility, low operating cost and simple operation.
  • the biochemical method is often caused. Nitrides in the effluent are often difficult to achieve compliance.
  • the conventional biochemical process for treating synthetic wastewater can effectively degrade the main components such as organic matter and suspended solids in the wastewater.
  • the main water quality indicators such as COD & , BOD 5 and SS can all be discharged to the standard, but in the synthetic leather wastewater.
  • the ammonia nitrogen and total nitrogen removal effects are unstable, and the ammonia nitrogen concentration in the effluent is difficult to achieve the standard discharge, which has become one of the important factors restricting the further engineering application of the conventional tannery wastewater treatment process.
  • the special physical and chemical reaction pretreatment unit plus conventional biochemical reaction process can effectively degrade the organic matter in the synthetic leather wastewater, and can also effectively degrade the ammonia nitrogen in the wastewater, but has high investment cost, long process flow, complicated technical operation and high running cost. It is difficult to be widely promoted and applied in the wastewater treatment of the tanning industry including synthetic leather.
  • the prior art has various biological treatment methods such as biological method, physicochemical method (adsorption, extraction), chemical method (catalytic oxidation, supercritical water oxidation, alkaline hydrolysis). .
  • the physicochemical method such as extraction and adsorption method treats DMF-containing wastewater.
  • the physicochemical unit process is mainly used for pretreatment of DMF-containing wastewater.
  • DMF wastewater by conventional aerobic activated sludge process is an economical and effective method. Since DMF is biodegradable, DMF can be used as the sole carbon source and nitrogen source to culture microorganisms under aerobic conditions. Microorganisms degrade DMF wastewater in aerobic, fermentation and nitrification environments at different concentrations and pH values. Under aerobic conditions DMF has the highest degradation rate and the product is NH 3 . Microorganisms or soil separated from soils frequently exposed to industrial wastewater near refinery and petrochemical plant installations are added to activated sludge to enrich, isolate and screen strains used to degrade DMF, such as Pseudomonas minuscula and Pcrucivial.
  • the object of the present invention is to overcome the deficiencies in the prior art for treating wastewater containing dimethylformamide synthetic leather, and to provide a biochemical method for treating waste water containing dimethylformamide synthetic leather, which integrates and strengthens the suspended filler flow.
  • the immobilized growth of the microbial surface of the chemical bed and the high bio-biomass of the membrane bioreactor have the advantages of high efficiency of separation of the mud and water, strengthen the effective degradation of DMF, and discharge the ammonia nitrogen of the effluent, which is an economy for the wastewater containing DMF synthetic leather. , efficient biochemical treatment.
  • a biochemical method for treating wastewater containing dimethylformamide synthetic leather of the present invention the steps of which are:
  • Step 1 The wastewater containing dimethylformamide synthetic leather to be treated is passed into a new membrane bioreactor of aerobic sludge-anaerobic filler structure to control the influent water quality index of synthetic leather wastewater to: CODcr is 166-1276 mg /L, ammonia nitrogen is 169-311 mg / L, total nitrogen is 203-360mg / L, the aerobic sludge - anaerobic filler structure of the new membrane bioreactor including aerobic zone and anaerobic zone, aerobic The zone and the anaerobic zone are integrated or separated, and the two zones are relatively closed;
  • Step 2 The wastewater containing dimethylformamide synthetic leather to be treated enters the aerobic zone first, and the aerobic zone adopts the specialized domestication of activated sludge with nitrifying bacteria as the dominant flora.
  • the acclimation period is 2-4 weeks, the main nitrogen
  • the source is various forms such as ammonium bicarbonate and ammonium chloride.
  • the separation membrane of the present invention uses a commercially available microfiltration membrane or ultrafiltration membrane module. ;
  • Step 3 The synthetic leather wastewater treated in the aerobic zone enters the anaerobic zone, and the anaerobic zone is filled with suspended filler.
  • the volume ratio is between 30 and 60%.
  • the agitation power is provided by a stirrer, and the immobilized anaerobic biofilm is used. Denitrification reaction, converting nitrate nitrogen in the synthetic leather wastewater refluxed from the aerobic zone to nitrogen;
  • Step 4 The synthetic leather wastewater treated by the anaerobic zone is sequentially discharged into a new membrane bioreactor of aerobic sludge-anaerobic filler structure.
  • the suspending filler in the third step is made of polyethylene, the appearance is an empty cylinder, the height is 7 mm, the diameter is 10 mm, the inner cross support, the outer fins, the density is less than water, the void ratio is 88%
  • the total specific surface area of the suspended filler is 690 m 2 /m 3
  • the effective specific surface area for biofilm attachment is 500 m 2 /m 3 .
  • the initial smoldering period of the aerobic sludge-anaerobic filler structure of the novel membrane bioreactor is 5 days, intermittent Water change, COD load is 0.6kg/m 3 ⁇ d, ammonia nitrogen load is 0.2kg/m 3 ⁇ d, total nitrogen load is 0.3kg/m 3 ⁇ d, after 10 days, increase 5% of water load per day, run Stable operation after 3 months.
  • the synthetic leather wastewater contains DMF (dimethylformamide), the DMF has a high nitrogen content, and one of the products of the biochemical degradation process is ammonia nitrogen.
  • the main improvement of the present invention is based on ammonia nitrogen aerobic nitrification and anaerobic nitrogen removal organisms. Degradation principle, a well-designed aerobic sludge-anaerobic filler structure of the new membrane bioreactor, making full use of the commercially available microfiltration membrane or ultrafiltration membrane module for good retention of microorganisms such as nitrifying bacteria, to achieve PU synthetic leather
  • the high-efficiency removal of ammonia nitrogen and total nitrogen in wastewater can achieve the discharge of synthetic leather wastewater.
  • the anaerobic part included in the present invention realizes nitriding and denitrification of DMF; the aerobic part mainly realizes nitrification of ammonia nitrogen by DMF conversion, and the suspension and separation membrane realize the whole biochemical process Strengthening effect.
  • the novel membrane bioreactor of the aerobic sludge-anaerobic filler structure of the invention comprises a two-stage biochemical reaction unit of an aerobic zone and an anaerobic zone, and integrates a membrane bioreactor and a suspended fluidized fluidized bed in a high-strength industry.
  • the aerobic zone uses aerobic activated sludge to achieve nitrification, converts ammonia nitrogen into nitrate nitrogen, and uses the mud-water separation function of the separation membrane to achieve low-concentration ammonia nitrogen, low suspended matter and chroma effluent;
  • the denitrification reaction is carried out by using an immobilized anaerobic biofilm, and the nitride in the wastewater from the aerobic zone is converted into nitrogen, and the synthetic leather wastewater is treated by a novel membrane bioreactor of an aerobic sludge-anaerobic filler structure.
  • a biochemical method for treating waste water containing dimethylformamide synthetic leather according to the present invention since a novel membrane bioreactor adopting an aerobic sludge-anaerobic filler structure can realize the discharge of organic substances in wastewater, Effectively decompose ammonia nitrogen in synthetic leather wastewater to achieve ammonia nitrogen discharge.
  • the ammonia nitrogen removal rate is about 95%
  • the effluent concentration is below 8mg/L
  • the total nitrogen removal rate is about 90%
  • the total nitrogen concentration of effluent is stable at 15mg/L.
  • the ammonia nitrogen and total nitrogen in the effluent can be stably reached the “Emission Standard for Pollutants in Synthetic Leather and Artificial Leather Industry” (GB21902-2008).
  • the emission standard of ammonia nitrogen and total nitrogen in tannery wastewater The concentration of synthetic leather wastewater in experimental treatment: CODcr 166-1276mg/L , ammonia nitrogen 169-311mg / L, total nitrogen 203- 360mg / L, effluent can be stabilized in: CODcr 39-58mg / L, ammonia nitrogen 4.2-7.4mg / L, total nitrogen 8.5-13.8mg / L;
  • the biochemical method for treating wastewater containing dimethylformamide synthetic leather of the present invention is compared with the characteristics of the A/0 process:
  • the conventional A/0 process connects the aerobic section of the front section and the aerobic section of the back section in series.
  • the A segment DO is not more than 0.2 mg/L, and the 0 segment DO is 2 to 4 mg/L.
  • heterotrophic bacteria hydrolyzes suspended pollutants and soluble organic matter such as starch, fiber and carbohydrate in sewage into organic acids, which decompose macromolecular organic matter into small molecular organic substances, and heterotrophic bacteria carry out pollutants such as protein and fat.
  • Ammoniation, free ammonia (NH 3 , NH 4 + ) ; nitrification of autotrophic bacteria in the aerobic section oxidizes NH 3 -N (NH 4 + ) to H0 3 _, and returns to the A pool by reflux control.
  • the denitrification of the anaerobic bacteria reduces N0 3 _ to molecular nitrogen (N 2 ) to complete the cycle of C, N, and 0 in the ecology, and realize the harmless treatment of sewage.
  • N 2 molecular nitrogen
  • A/0 process operation process control is prone to sludge bulking and loss, and the effect of nitrogen and phosphorus removal is poor.
  • MLSS should generally be above 3000mg/L, below which the A/0 system denitrification effect is significantly reduced.
  • the TN/MLSS loading rate in the nitrification reaction should be below 0.05gTN/(gMLSS ⁇ d), and above this value, the nitrification effect is poor.
  • the main factor affecting nitrification is the presence and activity of nitrifying bacteria, because the minimum specific growth rate of autotrophic nitrifying bacteria is 0.21/d , while the minimum specific proliferation rate of heterotrophic aerobic bacteria is 1.2/d.
  • the sludge age is required to be greater than 4.76d; therefore, the nitrifying bacteria can not have an advantage in the activated sludge, and when the ammonia nitrogen concentration is high, the nitrification effect is very poor;
  • the aerobic zone of the present invention can trap all microorganisms in the reactor, for microorganisms having a lower rate of growth,
  • the immobilized anaerobic biofilm is used for denitrification, and the nitrogen in the wastewater from the aerobic zone is converted into nitrogen, and the wastewater is treated by a novel membrane bioreactor of anaerobic-aerobic distribution.
  • FIG. 1 is a removal effect of a biochemical method for treating wastewater containing dimethylformamide synthetic leather to COD according to the present invention
  • FIG. 2 is a biochemical process for treating wastewater containing dimethylformamide synthetic leather according to the present invention
  • Method for removing total nitrogen
  • Figure 3 is a method for treating ammonia nitrogen removal by a biochemical method for treating wastewater containing dimethylformamide synthetic leather
  • Figure 4 is a structure of aerobic sludge-anaerobic filler in the present invention Schematic diagram of the novel membrane bioreactor;
  • Figure 5 is a cross-sectional view taken along line A-A of Figure 4.
  • Figure 6 is a cross-sectional view taken along line B-B of Figure 4.
  • a synthetic leather tanning company a large-scale enterprise with an annual output of 240,000 meters of PU leather, has a wastewater discharge of about 80,000 tons/year. Its wastewater characteristics are quite representative in the domestic tanning industry.
  • the original process is hydrolysis + contact oxidation + Coagulation and sedimentation, the water output index is ammonia nitrogen 150-180mg / L, of which ammonia nitrogen exceeds the standard.
  • the pollutants including total nitrogen and ammonia nitrogen can be discharged to the standard, and the specific processing steps are as follows:
  • Step 1 The wastewater containing dimethylformamide synthetic leather to be treated is passed into a new membrane bioreactor of aerobic sludge-anaerobic filler structure to control the influent water quality index of synthetic leather wastewater to: CODcr is 166-1276 mg /L, ammonia nitrogen is 169-311 mg / L, total nitrogen is 203-360mg / L, the influent water quality index in this example is shown in Table 1, the aerobic sludge - anaerobic filler structure of the new membrane
  • the bioreactor includes an aerobic zone 5 and an anaerobic zone 6, an aerobic zone 5 and an anaerobic zone 6-integrated or split-type design, and the two zones are relatively closed. Specifically, in combination with FIG. 4, FIG. 5 and FIG.
  • the novel membrane bioreactor of the aerobic sludge-anaerobic filler structure of the present invention comprises: an inlet pipe 1, an aeration pipe 2, a separation membrane 3, and a membrane support 4 , aerobic zone 5, anaerobic zone 6 and agitator 7,
  • the novel membrane bioreactor body comprises an aerobic zone 5 and an anaerobic zone 6, and the separation membrane 3 is fixed in the aerobic zone 5 through the membrane support 4, the agitator 7 is fixedly installed in the anaerobic zone 6, and aerated in the aerobic zone 5 through the aeration pipe 2.
  • the initial smoldering period of the aerobic sludge-anaerobic filler structure of the novel membrane bioreactor is 5 days, intermittent water exchange, COD
  • the load is 0.6kg/m 3 * d
  • the ammonia nitrogen load is 0.2kg/m 3 ⁇ d
  • the total nitrogen load is 0.3kg/m 3 ⁇ d.
  • the inflow load is increased by 5% every day, after running for 3 months. Stable operation.
  • Step 2 The dimethylformamide-containing synthetic leather wastewater to be treated first enters the aerobic zone 5, and the aerobic zone 5 adopts the specialized taming
  • the activated sludge with nitrifying bacteria as the dominant flora has a domestication cycle of 3 weeks.
  • the main nitrogen sources are various forms of compounds such as ammonium bicarbonate and ammonium chloride.
  • the aerobic zone 5 sludge reflux ratio is 200%. Achieve complete nitrogen removal of various forms of nitrogen such as ammonia nitrogen, and adjust the pH of the aerobic zone 5 to 8.5.
  • the aeration of the aerobic zone 5 is provided by the aeration pipe 2, and the nitrification reaction is realized by the aerobic activated sludge.
  • the ammonia nitrogen is converted into nitrate nitrogen, and the separation membrane 3 is used for slurry water separation.
  • the separation membrane 3 of the present invention employs a commercially available microfiltration membrane or ultrafiltration membrane module.
  • Step 3 The synthetic leather wastewater treated by the aerobic zone 5 enters the anaerobic zone 6, and the anaerobic zone 6 is filled with the suspended filler, and the volume ratio is between 45%.
  • the suspension filler in this embodiment is made of polyethylene.
  • the appearance is an empty cylinder with a height of 7mm, a diameter of 10mm, a cross support inside, a fin on the outside, a density less than water, a void ratio of 88%, and a total specific surface area of suspended filler of 690 m 2 /m 3 .
  • the effective specific surface area of the film adhesion is 500 m 2 /m 3
  • the stirring power is provided by the agitator 7
  • the denitrification reaction is carried out by using the immobilized anaerobic biofilm to convert the nitrate nitrogen in the synthetic leather wastewater refluxed from the aerobic zone 5 It is nitrogen.
  • Step 4 The synthetic leather wastewater treated by the anaerobic zone 6 is sequentially discharged into a novel membrane bioreactor of aerobic sludge-anaerobic filler structure, and the water quality index changes are shown in the following table.
  • Table 1 shows the average variation of water quality indicators in Example 1
  • a synthetic leather tannery company has a wastewater discharge of about 50,000 tons/year, and its ammonia nitrogen can not reach the standard for many years, and the ammonia nitrogen exceeds the standard.
  • the pollutant indicators including total nitrogen and ammonia nitrogen can be discharged to the standard, and the specific processing steps are as follows:
  • Step 1 The wastewater containing dimethylformamide synthetic leather to be treated is passed into a new membrane bioreactor of aerobic sludge-anaerobic filler structure to control the influent water quality index of synthetic leather wastewater to: CODcr is 166-1276 mg /L, ammonia nitrogen is 169-311 mg / L, total nitrogen is 203-360mg / L, the influent water quality index in this example is shown in Table 2, the aerobic sludge - anaerobic filler structure of the new membrane
  • the bioreactor includes an aerobic zone 5 and an anaerobic zone 6, an aerobic zone 5 and an anaerobic zone 6-integrated or split-type design, and the two zones are relatively closed. Specifically, in combination with FIG. 4, FIG. 5 and FIG.
  • the novel membrane bioreactor of the aerobic sludge-anaerobic filler structure of the present invention comprises: an inlet pipe 1, an aeration pipe 2, a separation membrane 3, and a membrane support 4 , aerobic zone 5, anaerobic zone 6 and agitator 7,
  • the novel membrane bioreactor body comprises an aerobic zone 5 and an anaerobic zone 6, and the separation membrane 3 is fixed in the aerobic zone 5 through the membrane support 4, the agitator 7 is fixedly installed in the anaerobic zone 6, and aerated in the aerobic zone 5 through the aeration pipe 2.
  • the initial smoldering period of the aerobic sludge-anaerobic filler structure of the novel membrane bioreactor is 5 days, intermittent water exchange, COD
  • the load is 0.6kg/m 3 * d
  • the ammonia nitrogen load is 0.2kg/m 3 ⁇ d
  • total nitrogen load is 0.3kg/m 3 ⁇ d
  • after 10 days increase the inflow load by 5% every day, and run stably after 3 months of operation.
  • Step 2 The wastewater containing dimethylformamide synthetic leather to be treated first enters the aerobic zone 5, and the aerobic zone 5 adopts an activated sludge which is exclusively acclimated with nitrifying bacteria as the dominant bacterial flora, and the activated sludge is from Hangzhou.
  • the aeration tank sludge of a synthetic leather wastewater has a domestication period of 2 weeks.
  • the main nitrogen sources are various forms of compounds such as ammonium bicarbonate and ammonium chloride.
  • the aerobic zone 5 sludge reflux ratio is 100%, and ammonia nitrogen is realized.
  • the separation membrane 3 of the present invention employs a commercially available microfiltration membrane or ultrafiltration membrane module.
  • Step 3 The synthetic leather wastewater treated by the aerobic zone 5 enters the anaerobic zone 6, and the anaerobic zone 6 is filled with the suspended filler, and the volume ratio is between 30%.
  • the suspension filler in this embodiment is made of polyethylene.
  • the appearance is an empty cylinder with a height of 7mm, a diameter of 10mm, a cross support inside, a fin on the outside, a density less than water, a void ratio of 88%, and a total specific surface area of suspended filler of 690 m 2 /m 3 .
  • the effective specific surface area of the film adhesion is 500 m 2 /m 3
  • the stirring power is provided by the agitator 7
  • the denitrification reaction is carried out by using the immobilized anaerobic biofilm to convert the nitrate nitrogen in the synthetic leather wastewater refluxed from the aerobic zone 5 It is nitrogen.
  • Step 4 The synthetic membrane wastewater treated by the anaerobic zone 6 is sequentially discharged into a novel membrane bioreactor of aerobic sludge-anaerobic filler structure, and the water quality index changes are shown in the following table.
  • a synthetic leather tannery company has a wastewater discharge of about 50,000 tons/year, and its ammonia nitrogen can not reach the standard for many years, and the ammonia nitrogen exceeds the standard.
  • the pollutant indicators including total nitrogen and ammonia nitrogen can be discharged to the standard, and the specific processing steps are as follows:
  • Step 1 The wastewater containing dimethylformamide synthetic leather to be treated is passed into a new membrane bioreactor of aerobic sludge-anaerobic filler structure to control the influent water quality index of synthetic leather wastewater to: CODcr is 166-1276 mg /L, ammonia nitrogen is 169-311 mg / L, total nitrogen is 203-360mg / L, the influent water quality indicators in this example are shown in Table 3, the aerobic sludge - anaerobic filler structure of the new membrane
  • the bioreactor includes an aerobic zone 5 and an anaerobic zone 6, an aerobic zone 5 and an anaerobic zone 6-integrated or split-type design, and the two zones are relatively closed. Specifically, in combination with FIG. 4, FIG. 5 and FIG.
  • the novel membrane bioreactor of the aerobic sludge-anaerobic filler structure of the present invention comprises: an inlet pipe 1, an aeration pipe 2, a separation membrane 3, and a membrane support 4 , aerobic zone 5, anaerobic zone 6 and agitator 7,
  • the novel membrane bioreactor body comprises an aerobic zone 5 and an anaerobic zone 6, and the separation membrane 3 passes through the membrane support 4 is fixed in the aerobic zone 5, the agitator 7 is fixedly installed in the anaerobic zone 6, and the aerobic zone 5 is aerated by the aeration pipe 2.
  • the initial smoldering period of the aerobic sludge-anaerobic filler structure of the novel membrane bioreactor is 5 days, intermittent water exchange, COD
  • the load is 0.6kg/m 3 * d
  • the ammonia nitrogen load is 0.2kg/m 3 ⁇ d
  • the total nitrogen load is 0.3kg/m 3 ⁇ d.
  • the inflow load is increased by 5% every day, after running for 3 months. Stable operation.
  • Step 2 The wastewater containing dimethylformamide synthetic leather to be treated first enters the aerobic zone 5, and the aerobic zone 5 is an activated sludge which is exclusively acclimated with nitrifying bacteria as the dominant bacterial flora, and the domestication cycle is 4 weeks.
  • the main nitrogen source is ammonium bicarbonate, ammonium chloride and other forms of compounds, control aerobic zone 5 sludge reflux ratio of 300%, to achieve complete nitrogen removal of various forms of nitrogen such as ammonia nitrogen, and regulate aerobic
  • the pH value of the zone 5 is 9, and the aeration of the aerobic zone 5 is provided by the aeration pipe 2, the nitrification reaction is performed by the aerobic activated sludge, the ammonia nitrogen is converted into the nitrate nitrogen, and the separation membrane 3 is used for the slurry water separation, the present invention
  • the separation membrane 3 in use is a commercially available microfiltration membrane or ultrafiltration membrane module.
  • Step 3 The synthetic leather wastewater treated by the aerobic zone 5 enters the anaerobic zone 6, and the anaerobic zone 6 is filled with the suspended filler, and the volume ratio is between 60%.
  • the suspension filler in this embodiment is made of polyethylene.
  • the appearance is an empty cylinder with a height of 7mm, a diameter of 10mm, a cross support inside, a fin on the outside, a density less than water, a void ratio of 88%, and a total specific surface area of suspended filler of 690 m 2 /m 3 .
  • the effective specific surface area of the film adhesion is 500 m 2 /m 3
  • the stirring power is provided by the agitator 7
  • the denitrification reaction is carried out by using the immobilized anaerobic biofilm to convert the nitrate nitrogen in the synthetic leather wastewater refluxed from the aerobic zone 5 It is nitrogen.
  • Step 4 The synthetic membrane wastewater treated by the anaerobic zone 6 is sequentially discharged with a new type of membrane bioreactor of aerobic sludge-anaerobic filler structure, and the water quality index changes are shown in the following table.
  • a biochemical method for treating waste water containing dimethylformamide synthetic leather of the present invention the main technical advantages thereof can be concentrated as follows: According to the application of the present invention, in addition to the normal removal of organic substances and the like, the synthetic leather wastewater containing DMF can be made. Total nitrogen and ammonia nitrogen have reached the “Emission Standard for Pollutants in Synthetic Leather and Artificial Leather Industry” (GB21902-2008). The emission standards for ammonia nitrogen and total nitrogen in tannery wastewater.
  • the treatment effect of the method of the present invention on wastewater containing dimethylformamide synthetic leather will be described below in conjunction with a typical test operation.
  • the new membrane bioreactor of the aerobic sludge-anaerobic filler structure of the present invention was used for a continuous operation test for a tanning company sewage treatment plant for more than three months. The test showed that the new membrane bioreactor treated the synthetic leather wastewater. The effect is remarkable, especially the treatment effect of total nitrogen and ammonia nitrogen is relatively stable.
  • 1 is the removal effect of COD according to the present invention. It can be seen from FIG.
  • phase 1 that: in the startup phase (ie: phase 1), the influent COD decreases from 1276.2 mg/L to 210.9 mg/L, and the effluent COD is from Between 100mg/L and 158mg/L, although the effluent COD is greater than 100mg/L, in the start-up phase, the overall COD removal rate is decreasing, and the average removal rate is only 64.3%.
  • phase 2 In the stable operation phase (ie: phase 2) (33d ⁇ 105d), the influent COD is maintained at 358.8mg/L on average, and the effluent COD is on average at 45.5mg/L.
  • the COD removal rate of the method of the present invention averages 72.4%.
  • the effluent COD is basically less than 50 mg/L.
  • the concentration of total nitrogen in the effluent is less than 10 mg/L, which meets the emission standard for total nitrogen in tannery wastewater.
  • FIG. 3 is the effect of removing ammonia nitrogen according to the present invention. It can be seen from FIG. 3 that the method of the present invention has an obvious effect on ammonia nitrogen removal, and the effluent ammonia nitrogen is less than 15 mg/L after stabilization.

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Abstract

本发明公开了一种处理含二甲基甲酰胺合成革废水的生化方法，属于废水处理领域。其步骤为：将待处理的合成革废水通入好氧污泥-厌氧填料结构的新型膜生物反应器，该新型膜生物反应器包括好氧区和厌氧区；待处理的合成革废水先进入好氧区，好氧区采用专性驯化以硝化菌为优势菌群的活性污泥，控制好氧区污泥回流比为100-300%，并调节好氧区的pH值为8-9；经过好氧区处理后的合成革废水进入厌氧区，厌氧区填充悬浮填料，容积比为30-60%之间；经过厌氧区处理后的合成革废水排出好氧污泥-厌氧填料结构的新型膜生物反应器。采用本发明的方法，出水氨氮和总氮可以稳定达到《合成革与人造革工业污染物排放标准》（GB21902-2008）的排放标准。

Description

一种处理含二甲基甲酰胺合成革废水的生化方法 技术领域
[0001] 本发明涉及合成革与制革废水处理技术领域， 更具体地说， 本发明涉及一种处理含 二甲基甲酰胺合成革废水的生化方法。
背景技术
[0002] 合成革废水一般来源于以下几股废水： 水糅废水， CODcr300~1500 mg/L之间， 氨氮 小于 50 mg/L; 洗槽水， CODcrl0000~20000 mg/L之间， 此废水进入回收系统； 洗塔废水， CODcr5000~20000 mg/L之间， 氨氮小于 100 mg/L; 塔顶水， 作为产品生产用水， 因此此类 废水基本不排放； 地面水及洗桶水， CODcrl0000~20000 mg/L; 喷涂水， 非常难处理， 非连 续排放。
[0003】 PU合成革的表面处理过程中使用 DMF (二甲基甲酰胺）， DMF化学式 (CH3)2NHCHO， 化学性质稳定， 且有毒性， 我国地面水中最高容许质量浓度推荐值是 25 mg/L。 DMF在合成 革生产上仅作为有机溶剂， 不参与制革工艺的化学反应过程， 因此， 大量的 DMF将主要进 入合成革废水中， 而 DMF在生化等降解过程中将产生大量的氨氮， 相比传统的合成革废水， 由于合成革废水中对微生物具有抑制作用的成分较多， 合成革废水中的氨氮更难有效削除和 降解， 因此， 合成革废水处理中主要难点是 DMF 的有效降解， 即使在 COD等常规指标达 标情况下， 出水中氨氮浓度水平也往往波动很大， 很难满足 《合成革与人造革工业污染物排 放标准》 （GB21902-2008)。
[0004] 氨氮是合成革废水中的主要污染成分之一， 目前常规制革废水处理工艺中所产生的 氨氮超标排放往往将导致严重的水体富营养化状况， 引起生态环境的持续恶化。 据湖北科亮 生物工程有限公司的监测报道， 离子态氨氮毒性较弱， 非离子态的 NH3-N 则毒性较强， NH3-N会通过鳃皮膜进入鱼体， 直接增加水产动物排除废氮的负担， 往往结果导致水生生物 体内多种酶活性受到抑制， 降低血液的输氧能力， 导致氧气和废物交换不畅而窒息， 因此， 水体中的氨氮将严重损害各种生物赖以生存的环境质量。
[0005] 目前， 专门针对工业废水中较高浓度氨氮有效降解， 已经有化学沉淀法、 吹脱法、 离子交换法、 膜法、 催化氧化法、 电化学法和臭氧氧化等各种技术手段。
[0006] 化学沉淀法多采用 MgCl2 · 6H20 禾卩 Na2HP04 · 12H20 或 MgO和 H3P04 使 NH4 +-
N 生成磷酸铵镁沉淀， 经重力沉淀或过滤后分离， 从而达到去除氨氮的目的。 《重庆环境科 学》 2000 ,22 (6) :54~56钟理， 詹怀宇等 "化学沉淀法除去废水中的氨氮及其反应的探讨"， 研究了 MAP 法对屠宰废水、 制革废水、 垃圾渗滤液氨氮含量高的废水的处理， 虽然 MAP 沉淀法具有较好处理效果， 但处理费用较高， 使得在制革废水处理中应用不经济。
[0007] 吹脱法是实际工程中除氨氮常用方法之一， 《科技情报开发与经济》 1995 ,5 (1) ： 20-21 温俨， 张晓丽， 崔桂芬： "吹脱法去除废水中氨氮的试验研究"， 发现吹脱法对氨氮去 除率一般是 30%〜50%， 含氮量特别高的废水去除率可以达到 90%， 对于含氨氮量较高的制 革废水经过吹脱处理仍然达不到排放要求， 且运行费用不菲。
[0008] 《中国皮革》 2001,30 ( 13 ) :23-27温祖谋， 李清， 沉钧： "制革污水处理工艺技术的 研究"， 研究了用次氯酸钠作为氧化剂去除制革污水中氨氮， 氨氮去除率约 80%， 次氯酸钠 用量以 NaC10:NH3计约为 6.5~8.0： 1， 由此可见氧化法要达到较理想的处理效果， 氧化剂用 量要大， 导致运行费用较高， 作为常规处理不经济。
[0009] 离子交换法是通过离子树脂上的阳离子与废水中的氨氮离子进行交换， 离子交换树 脂材料一般常用沸石、 活化沸石。 《非金属矿》 2009,32(2)， 68-71 丁绍兰、 李玲、 雷小利等: "天然沸石和合成沸石去除制革废水氨态氮的研究"， 研究表明： 沸石对制革废水中的氨氮 有较好的吸附去除， 但该方法的去除效果容易受废水中含盐量的影响， 且目前离子交换法多 应用于氨氮含量较低的水处理中， 由于离子交换树脂一般都需要交换能力恢复再生等化学过 程， 直接用于高浓度的工业废水处理还比较困难。
[0010] 此外， 也有采取回收法， 例如中国专利 CN201840908U 萃取回收， 但操作较为复杂。 微生物分解， 例如中国专利 CN101935626A、 CN101914479A, 但需要纯菌分离、 富集和放 大等复杂操作过程。
[0011] 合成革废水中的氨氮主要来源于 DMF (二甲基甲酰胺） 的生化降解过程， 因此， 合 成革废水中氮的去除效果一般应该包括： DMF 的降解过程和氨氮的去除过程两个方面。 针 对废水中 DMF的处理和回收， 有下面相关专利涉及。
[0012] 中国专利 CN101074120 —种新的有机废水的处理和资源化的技术， 特别是含苯酚、 苯胺、 甲苯、 四氢呋喃、 环己醇、 N， N—二甲基甲酰胺、 乙腈、 甲醇、 乙醇、 甲酸等生物 难降解有机质的有机废水的处理和资源化技术。 以含苯酚、 苯胺、 甲苯、 四氢呋喃、 环己醇、 N， N—二甲基甲酰胺、 乙腈、 甲醇、 乙醇、 甲酸等有机质中的一种或两种或两种以上的有 机废水为原料， 在雷尼镍催化剂作用下， 在 180~350°C的温度和 l~16MPa压力下， 由废水 中的有机质在催化剂作用下和水发生重整反应， 生成氢气、 甲垸、 二氧化碳和一氧化碳。 但 整个处理过程需要加压、 加温和催化操作， 对有机废水的处理而言， 工艺过程操作参数苛刻， 成本较高。 [0013] 中国专利 CN101274169合成革 DMF废液精馏回收预处理方法， 包括如下步骤： （1 ) 收集的 DMF废液经由输液泵打入粗滤器进行一级分离， 所述的粗滤器规格为： 150-200 目； (2) 经一级分离后的 DMF 废液进入沉降离心机进行二级分离， 所述的沉降离心机的分离 因素为： 3000-11000; (3 ) 上述一、 二级分离所产生的固体废渣进行焚烧或作为燃料。 本处 理过程的重点在于对回收过程中 DMF杂质的预处理。
[0014] 中国专利 CN1982223 合成革废水回用方法， 包括如下步骤： （1 ) 首先进行过滤预处 理， 使用微孔过滤方法， 除去水中细小悬浮物， 作为预处理手段， 保护主体反应区， 压力为 0.05~0.2MPa, 有效过滤孔径为 5~10 μ m; (2) 再使用催化剂， 在 80-95°C， 10-20m/hr流速， 3-6/h 空速下， 进行选择性吸附-催化反应处理； （3 ) 最后进行精密过滤处理， 其有效过滤孔 径 1~2 μ ηι。 但整个处理过程需要控温、 吸附和催化操作， 对有机废水的处理而言， 工艺过 程操作参数苛刻， 成本较高。
[0015] 目前已有的处理 PU合成革废水工艺主要有物理化学法和生物法两大类， 虽然吹脱、 沉淀、 膜吸收和湿式氧化等物化除氮措施效率较高， 但通常只是对氨氮进行了多种形式的相 转移， 仅仅从液相中转移到大气或固相中， 并带来相应的环境处置成本和二次污染， 而通常 留在母液中的氨氮浓度仍将高达 20~100mg/L 之间。 生化过程可以有效地削除制革废水中的 有机污染物， 具有环境相溶性高、 运行成本低和操作简单等优点， 但由于制革废水中多种成 分对硝化过程的抑制作用， 往往导致生化法出水中的氮化物往往难以实现达标排放。
[0016] 针对常规生化工艺处理合成革废水可以有效降解废水中的有机物和悬浮物等主要成 分， 主要水质指标如 COD&、 BOD5、 SS等可以都做到达标排放， 但对合成革废水中的氨氮 和总氮去除效果不稳定， 出水中的氨氮浓度难以实现达标排放， 成为制约常规制革废水处理 工艺进一步工程应用的重要因素之一。 针对专门物化预处理单元加常规生化反应工艺， 可以 有效降解合成革废水中的有机物， 同时也可以有效降解废水中的氨氮， 但存在投资成本高、 工艺流程较长、 技术操作复杂和运行成本高等特点， 难以在包括合成革在内的制革行业的废 水治理中得到普遍的推广和应用。
[0017] 专门针对 PU合成革废水中含有的 DMF， 现有技术已有生物法、 物化法 （吸附、 萃 取）、 化学法 （催化氧化、 超临界水氧化、 碱性水解） 等多种处理技术。 萃取、 吸附法等物 化方法处理含 DMF废水， 相较生化法， 物化单元工艺主要用于含 DMF废水的预处理。
[0018] 应用传统的好氧活性污泥法处理 DMF 废水是一种经济、 有效的好方法。 由于 DMF 是可生物降解的， 在好氧条件下可以用 DMF 作唯一碳源和氮源来培养微生物； 微生物分别 在好氧、 发酵和硝化环境中， 不同浓度、 不同 pH值条件下降解 DMF废水， 在好氧条件下 DMF 降解率最高， 产物为 NH3。 用炼油厂、 石化厂装置附近经常接触工业废水的土壤中分 离出的微生物或泥土加到活性污泥中去， 富集、 分离和筛选用于降解 DMF 的菌种， 如 Pseudomonas minuscula和 Pcrucivial, 都可以实现对废水中所含有的 DMF的专性和高效降解。 但这些生化方法在处理 PU合成革废水中的 DMF氮化的过程中， 都存在培养条件苛刻、 工 艺流程长、 氨氮硝化程度低等不可避免的缺陷。
[0019] 目前包括合成革废水在内的制革废水的处理， 较常用工艺是将生物法和物化法相结 合， 但传统生物处理主要针对废水中高负荷 COD及其他杂质， 对氨氮处理效果往往不理想。
《江苏环境科技》 1998, 2 : 11-13. 张仁瑞， 杨伟华： "气浮-生化-气浮法处理合成革废水"， 发现由于制革废水中 Cr3+、 S2—等物质对微生物毒性抑制作用， 氨氮的浓度不降反升。 《环境 污染与防治》 2009,31 ( 3 ) 48-51 , 邓海华、 沈滨等： "曝气生物流化池生物强化处理高氨氮 制革废水研究"， 通过投加高效脱氮微生物菌剂的生物强化技术处理高氨氮废水， 处理高氨 氮制革废水取得了较好的处理效果， 但该工艺需大量高效菌种， 但特性高效菌种的培养需要 较高的生产成本。 但生物法处理制革废水氨氮在工程实际是最为可行的方法， 尤其水量较大 时运用生物法更为经济实用， 所以改良传统生物法， 克服原有生物法的弊端， 研发经济有效 地生物除氮工艺是势在必行。
发明内容
[0020] 发明要解决的技术问题
本发明目的在于克服现有技术中对含二甲基甲酰胺合成革废水处理的不足， 提供了一种处理 含二甲基甲酰胺合成革废水的生化方法， 本发明集成与强化了悬浮填料流化床微生物表面固 定化富集生长和膜生物反应器生物量高、 泥水分离效率高的优点， 强化了对 DMF 的有效降 解， 使出水氨氮达标排放， 是一种针对含 DMF合成革废水的经济、 高效的生化处理方法。
[0021] 技术方案
为达到上述目的， 本发明提供的技术方案为：
本发明的一种处理含二甲基甲酰胺合成革废水的生化方法， 其步骤为：
步骤一： 将待处理的含二甲基甲酰胺合成革废水通入好氧污泥-厌氧填料结构的新型膜生物 反应器， 控制合成革废水的进水水质指标至： CODcr为 166-1276mg/L， 氨氮为 169-311 mg/L， 总氮为 203-360mg/L， 所述的好氧污泥 -厌氧填料结构的新型膜生物反应器包括好氧区和厌氧 区， 好氧区和厌氧区一体化集成或分置式设计， 两区相对封闭运行；
步骤二： 待处理的含二甲基甲酰胺合成革废水先进入好氧区， 好氧区采用专性驯化以硝化菌 为优势菌群的活性污泥， 驯化周期为 2-4周， 主要氮源为碳酸氢铵、 氯化铵等多种形式的化 合物， 控制好氧区污泥回流比为 100-300%， 实现氨氮等各种形式的氮化物的完全脱氮， 并 调节好氧区的 pH值为 8-9， 好氧区的搅拌由曝气管提供， 利用好氧活性污泥实现硝化反应， 将氨氮转化为硝酸盐氮， 并利用分离膜进行泥水分离， 本发明中的分离膜采用已经商品化的 微滤膜或超滤膜组件；
步骤三： 经过好氧区处理后的合成革废水进入厌氧区， 厌氧区填充悬浮填料， 容积比为 30- 60%之间， 搅拌动力由搅拌器提供， 利用固定化厌氧生物膜进行反硝化反应， 将回流自好氧 区的合成革废水中的硝酸盐氮转化为氮气；
步骤四： 经过厌氧区处理后的合成革废水按序排出好氧污泥-厌氧填料结构的新型膜生物反 应器。
[0022] 优选地， 步骤三中的悬浮填料为聚乙烯材质， 外观呈空圆柱体， 高为 7mm， 直径为 10mm, 内部有十字支撑， 外部有翅片， 密度小于水， 空隙率达 88%， 悬浮填料总比表面积 为 690 m2/m3， 供生物膜附着的有效比表面积为 500m2/m3。
[0023] 优选地， 步骤一中通入待处理的含二甲基甲酰胺合成革废水前， 好氧污泥-厌氧填料 结构的新型膜生物反应器的初期闷曝期为 5天， 间歇换水， COD负荷为 0.6kg/m3 · d， 氨氮 负荷为 0.2kg/m3 · d， 总氮负荷为 0.3kg/m3 · d， 10天后， 每天提高 5%的进水负荷， 运行 3 个月后稳定运行。
[0024] 合成革废水中含有 DMF (二甲基甲酰胺）， DMF 含氮量高， 生化降解过程产物之一 就是氨氮， 本发明的主要改进是充分基于氨氮好氧硝化、 厌氧脱氮生物降解原理， 设计合理 的好氧污泥-厌氧填料结构的新型膜生物反应器， 充分利用已经商品化的微滤膜或超滤膜组 件对硝化菌等微生物良好的截留作用， 实现 PU合成革废水中氨氮和总氮的高效去除， 实现 合成革废水的达标排放。 具体说， 本发明包括的厌氧部分， 实现对 DMF 的氮化和反硝化作 用； 好氧部分， 主要实现由 DMF转化产生氨氮的硝化作用， 而悬浮填料和分离膜则是实现 对整个生化过程的强化作用。 本发明中好氧污泥-厌氧填料结构的新型膜生物反应器， 由好 氧区和厌氧区两级生化反应单元构成， 集成了膜生物反应器和悬浮填料流化床在高强度工业 废水中的技术优势。 其中好氧区利用好氧活性污泥实现硝化反应， 将氨氮转化为硝酸盐氮， 并利用分离膜膜的泥水分离功能实现低浓度氨氮、 低悬浮物和色度的出水； 而厌氧区则利用 固定化厌氧生物膜进行反硝化反应， 将回流自好氧区的废水中的氮化物转化为氮气， 合成革 废水经过好氧污泥-厌氧填料结构的新型膜生物反应器的处理， 在实现有机物稳定去除的同 时， 也可以实现氨氮等氮化物的达标排放， 并体现出运行成本低、 结构紧凑、 自动化程度高 等优点。 [0025] 有益效果
采用本发明提供的技术方案， 与已有的公知技术相比， 具有如下显著效果：
( 1 ) 本发明的一种处理含二甲基甲酰胺合成革废水的生化方法， 由于采用好氧污泥-厌氧填 料结构的新型膜生物反应器， 在实现废水中有机物达标排放同时， 可以有效降解合成革废水 中的氨氮， 实现氨氮的达标排放， 氨氮去除率达到 95%左右， 出水浓度 8mg/L 以下， 总氮 的去除率达到 90%左右， 出水的总氮浓度稳定在 15mg/L 以下， 出水氨氮和总氮可以稳定达 到 《合成革与人造革工业污染物排放标准》 （GB21902-2008 ) 制革废水氨氮、 总氮的排放标 准， 实验处理合成革废水浓度： CODcr 166-1276mg/L , 氨氮 169-311mg/L， 总氮 203- 360mg/L, 出水可以稳定在： CODcr 39-58mg/L， 氨氮 4.2-7.4mg/L， 总氮 8.5-13.8mg/L;
(2) 本发明的一种处理含二甲基甲酰胺合成革废水的生化方法相比 A/0工艺的特点： 常规 A/0 工艺将前段缺氧段和后段好氧段串联在一起， A 段 DO 不大于 0.2mg/L， 0 段 DO=2〜4mg/L。 在缺氧段异养菌将污水中的淀粉、 纤维、 碳水化合物等悬浮污染物和可溶性 有机物水解为有机酸， 使大分子有机物分解为小分子有机物， 异养菌将蛋白质、 脂肪等污染 物进行氨化作用， 游离出氨 （NH3、 NH4 +); 在好氧段自养菌的硝化作用将 NH3-N (NH4 +) 氧化为 H03_， 通过回流控制返回至 A池， 在缺氧条件下， 异氧菌的反硝化作用将 N03_还原 为分子态氮 （N2) 完成 C、 N、 0在生态中的循环， 实现污水无害化处理， 目前 A/0工艺已 经是一般城市或工业污水中比较普遍采用的工艺。 但采用 A/0工艺具有一定的局限性： A/0 工艺运行过程控制容易产生污泥膨胀和流失， 脱氮除磷效果较差。 MLSS —般应在 3000mg/L 以上， 低于此值 A/0系统脱氮效果明显降低。 在硝化反应中 TN/MLSS负荷率应 在 0.05gTN/(gMLSS · d)之下， 高于此值则硝化效果较差。 在硝化反应中， 影响硝化的主要 因素是硝化菌的存在和活性， 因为自氧型硝化菌最小比增长速度为 0.21/d; 而异养型好氧菌 的最小比增殖速度为 1.2/d。 要使硝化菌存活并占优势， 要求污泥龄大于 4.76d; 所以硝化菌 不能在活性污泥中占有优势， 当氨氮浓度较高时， 硝化效果很差；
而本发明的好氧区可以将所有的微生物都截留在反应器内， 对于比增长速率低的微生物，
(如硝化菌） 具有很好的富集效果， 因此， 对污水中较高浓度的氨氮具有很好的去除效果， 另外， 由于分离膜 （微滤膜或超滤膜） 可以将所有的污泥都全部截留在反应器内， 因此， 反 应器内具有较高的生物量， 因此具有对废水更高的去除潜力。 而厌氧区则利用固定化厌氧生 物膜进行反硝化反应， 将回流自好氧区的废水中的氮化物转化为氮气， 废水经过厌氧 -好氧 分布的新型膜生物反应器的处理， 在实现有机物稳定去除的同时， 也可以实现氨氮等氮化物 的达标排放。 相对于传统的 A/0 工艺， 则体现出对有机物降解效率高、 抗冲击负荷大、 不 易污泥膨胀、 除氮效果好、 结构紧凑和自动化程度高等优点。
附图说明
[0026] 图 1为本发明的一种处理含二甲基甲酰胺合成革废水的生化方法对 COD的去除效果; 图 2为本发明的一种处理含二甲基甲酰胺合成革废水的生化方法对总氮的去除效果； 图 3为本发明的一种处理含二甲基甲酰胺合成革废水的生化方法对氨氮的去除效果； 图 4为本发明中好氧污泥-厌氧填料结构的新型膜生物反应器的结构示意图；
图 5为图 4中的 A-A剖视图；
图 6为图 4中的 B-B剖视图。
[0027] 示意图中的标号说明如下： 1、 进水管； 2、 曝气管； 3、 分离膜； 4、 膜支架； 5、 好 氧区； 6、 厌氧区； 7、 搅拌器。
具体实施方式
[0028] 为进一步了解本发明的内容， 结合附图和实施例对本发明作详细描述。
[0029] 实施例 1
某合成革制革公司， 年产 24万米 PU革的规模企业， 废水排放量约 8万吨 /年， 其废水特征 在国内制革行业具有相当的代表性， 原始工艺为水解 +接触氧化 +混凝沉淀， 出水指标为氨氮 150-180mg/L, 其中氨氮超标严重。 但是应用本发明的生化方法， 包括总氮、 氨氮在内的污 染物指标均可达标排放， 具体处理步骤为：
步骤一： 将待处理的含二甲基甲酰胺合成革废水通入好氧污泥-厌氧填料结构的新型膜生物 反应器， 控制合成革废水的进水水质指标至： CODcr为 166-1276mg/L， 氨氮为 169-311 mg/L， 总氮为 203-360mg/L均可， 本实施例中进水水质指标如表 1 所示， 该好氧污泥 -厌氧填料结 构的新型膜生物反应器包括好氧区 5和厌氧区 6， 好氧区 5和厌氧区 6—体化集成或分置式 设计， 两区相对封闭运行。 具体结合图 4、 图 5和图 6所示， 本发明中的好氧污泥-厌氧填料 结构的新型膜生物反应器包括： 进水管 1、 曝气管 2、 分离膜 3、 膜支架 4、 好氧区 5、 厌氧 区 6和搅拌器 7， 该新型膜生物反应器主体包括好氧区 5和厌氧区 6， 分离膜 3通过膜支架 4固定在好氧区 5内， 搅拌器 7固定安装在厌氧区 6内， 好氧区 5中通过曝气管 2进行曝气。 本实施例中在通入待处理的含二甲基甲酰胺合成革废水前， 好氧污泥-厌氧填料结构的新型 膜生物反应器的初期闷曝期为 5 天， 间歇换水， COD 负荷为 0.6kg/m3 * d， 氨氮负荷为 0.2kg/m3 · d， 总氮负荷为 0.3kg/m3 · d， 10天后， 每天提高 5%的进水负荷， 运行 3个月后 稳定运行。
[0030] 步骤二： 待处理的含二甲基甲酰胺合成革废水先进入好氧区 5， 好氧区 5采用专性驯 化以硝化菌为优势菌群的活性污泥， 驯化周期为 3周， 主要氮源为碳酸氢铵、 氯化铵等多种 形式的化合物， 控制好氧区 5污泥回流比为 200%， 实现氨氮等各种形式的氮化物的完全脱 氮， 并调节好氧区 5的 pH值为 8.5， 好氧区 5的搅拌由曝气管 2提供， 利用好氧活性污泥 实现硝化反应， 将氨氮转化为硝酸盐氮， 并利用分离膜 3进行泥水分离， 本发明中的分离膜 3采用已经商品化的微滤膜或超滤膜组件。
[0031] 步骤三： 经过好氧区 5处理后的合成革废水进入厌氧区 6， 厌氧区 6填充悬浮填料， 容积比为 45%之间， 本实施例中的悬浮填料为聚乙烯材质， 外观呈空圆柱体， 高为 7mm， 直径为 10mm， 内部有十字支撑， 外部有翅片， 密度小于水， 空隙率达 88%， 悬浮填料总比 表面积为 690 m2/m3， 供生物膜附着的有效比表面积为 500m2/m3， 搅拌动力由搅拌器 7提供， 利用固定化厌氧生物膜进行反硝化反应， 将回流自好氧区 5的合成革废水中的硝酸盐氮转化 为氮气。
[0032] 步骤四： 经过厌氧区 6 处理后的合成革废水按序排出好氧污泥-厌氧填料结构的新型 膜生物反应器， 水质指标变化如下表所示。
[0033] 表 1 实施例 1的水质指标平均变化情况
Figure imgf000010_0001
实施例 2
某合成革制革公司， 废水排放量约 5 万吨 /年， 其废水氨氮常年不能稳定达标， 其中氨氮超 标严重。 应用本发明的生化方法， 包括总氮、 氨氮在内的污染物指标均可达标排放， 具体处 理步骤为：
步骤一： 将待处理的含二甲基甲酰胺合成革废水通入好氧污泥-厌氧填料结构的新型膜生物 反应器， 控制合成革废水的进水水质指标至： CODcr为 166-1276mg/L， 氨氮为 169-311 mg/L， 总氮为 203-360mg/L均可， 本实施例中进水水质指标如表 2所示， 该好氧污泥 -厌氧填料结 构的新型膜生物反应器包括好氧区 5和厌氧区 6， 好氧区 5和厌氧区 6—体化集成或分置式 设计， 两区相对封闭运行。 具体结合图 4、 图 5和图 6所示， 本发明中的好氧污泥-厌氧填料 结构的新型膜生物反应器包括： 进水管 1、 曝气管 2、 分离膜 3、 膜支架 4、 好氧区 5、 厌氧 区 6和搅拌器 7， 该新型膜生物反应器主体包括好氧区 5和厌氧区 6， 分离膜 3通过膜支架 4固定在好氧区 5内， 搅拌器 7固定安装在厌氧区 6内， 好氧区 5中通过曝气管 2进行曝气。 本实施例中在通入待处理的含二甲基甲酰胺合成革废水前， 好氧污泥-厌氧填料结构的新型 膜生物反应器的初期闷曝期为 5 天， 间歇换水， COD 负荷为 0.6kg/m3 * d， 氨氮负荷为 0.2kg/m3 · d， 总氮负荷为 0.3kg/m3 · d， 10天后， 每天提高 5%的进水负荷， 运行 3个月后 稳定运行。
[0034] 步骤二： 待处理的含二甲基甲酰胺合成革废水先进入好氧区 5， 好氧区 5采用专性驯 化以硝化菌为优势菌群的活性污泥， 活性污泥来自杭州某合成革废水的曝气池污泥， 驯化周 期为 2周， 主要氮源为碳酸氢铵、 氯化铵等多种形式的化合物， 控制好氧区 5污泥回流比为 100%， 实现氨氮等各种形式的氮化物的完全脱氮， 并调节好氧区 5的 pH值为 8， 好氧区 5 的搅拌由曝气管 2提供， 利用好氧活性污泥实现硝化反应， 将氨氮转化为硝酸盐氮， 并利用 分离膜 3进行泥水分离， 本发明中的分离膜 3采用已经商品化的微滤膜或超滤膜组件。
[0035] 步骤三： 经过好氧区 5处理后的合成革废水进入厌氧区 6， 厌氧区 6填充悬浮填料， 容积比为 30%之间， 本实施例中的悬浮填料为聚乙烯材质， 外观呈空圆柱体， 高为 7mm， 直径为 10mm， 内部有十字支撑， 外部有翅片， 密度小于水， 空隙率达 88%， 悬浮填料总比 表面积为 690 m2/m3， 供生物膜附着的有效比表面积为 500m2/m3， 搅拌动力由搅拌器 7提供， 利用固定化厌氧生物膜进行反硝化反应， 将回流自好氧区 5的合成革废水中的硝酸盐氮转化 为氮气。
[0036] 步骤四： 经过厌氧区 6 处理后的合成革废水按序排出好氧污泥-厌氧填料结构的新型 膜生物反应器， 水质指标变化如下表所示。
[0037] 表 2 实施例 2的水质指标变化情况
Figure imgf000011_0001
实施例 3
某合成革制革公司， 废水排放量约 5 万吨 /年， 其废水氨氮常年不能稳定达标， 其中氨氮超 标严重。 应用本发明的生化方法， 包括总氮、 氨氮在内的污染物指标均可达标排放， 具体处 理步骤为：
步骤一： 将待处理的含二甲基甲酰胺合成革废水通入好氧污泥-厌氧填料结构的新型膜生物 反应器， 控制合成革废水的进水水质指标至： CODcr为 166-1276mg/L， 氨氮为 169-311 mg/L， 总氮为 203-360mg/L均可， 本实施例中进水水质指标如表 3 所示， 该好氧污泥 -厌氧填料结 构的新型膜生物反应器包括好氧区 5和厌氧区 6， 好氧区 5和厌氧区 6—体化集成或分置式 设计， 两区相对封闭运行。 具体结合图 4、 图 5和图 6所示， 本发明中的好氧污泥-厌氧填料 结构的新型膜生物反应器包括： 进水管 1、 曝气管 2、 分离膜 3、 膜支架 4、 好氧区 5、 厌氧 区 6和搅拌器 7， 该新型膜生物反应器主体包括好氧区 5和厌氧区 6， 分离膜 3通过膜支架 4固定在好氧区 5内， 搅拌器 7固定安装在厌氧区 6内， 好氧区 5中通过曝气管 2进行曝气。 本实施例中在通入待处理的含二甲基甲酰胺合成革废水前， 好氧污泥-厌氧填料结构的新型 膜生物反应器的初期闷曝期为 5 天， 间歇换水， COD 负荷为 0.6kg/m3 * d， 氨氮负荷为 0.2kg/m3 · d， 总氮负荷为 0.3kg/m3 · d， 10天后， 每天提高 5%的进水负荷， 运行 3个月后 稳定运行。
[0038] 步骤二： 待处理的含二甲基甲酰胺合成革废水先进入好氧区 5， 好氧区 5采用专性驯 化以硝化菌为优势菌群的活性污泥， 驯化周期为 4周， 主要氮源为碳酸氢铵、 氯化铵等多种 形式的化合物， 控制好氧区 5污泥回流比为 300%， 实现氨氮等各种形式的氮化物的完全脱 氮， 并调节好氧区 5的 pH值为 9， 好氧区 5的搅拌由曝气管 2提供， 利用好氧活性污泥实 现硝化反应， 将氨氮转化为硝酸盐氮， 并利用分离膜 3进行泥水分离， 本发明中的分离膜 3 采用已经商品化的微滤膜或超滤膜组件。
[0039] 步骤三： 经过好氧区 5处理后的合成革废水进入厌氧区 6， 厌氧区 6填充悬浮填料， 容积比为 60%之间， 本实施例中的悬浮填料为聚乙烯材质， 外观呈空圆柱体， 高为 7mm， 直径为 10mm， 内部有十字支撑， 外部有翅片， 密度小于水， 空隙率达 88%， 悬浮填料总比 表面积为 690 m2/m3， 供生物膜附着的有效比表面积为 500m2/m3， 搅拌动力由搅拌器 7提供， 利用固定化厌氧生物膜进行反硝化反应， 将回流自好氧区 5的合成革废水中的硝酸盐氮转化 为氮气。
[0040] 步骤四： 经过厌氧区 6 处理后的合成革废水按序排出好氧污泥-厌氧填料结构的新型 膜生物反应器， 水质指标变化如下表所示。
[0041] 表 3 实施例 3的水质指标变化情况
Figure imgf000012_0001
本发明的一种处理含二甲基甲酰胺合成革废水的生化方法， 其主要的技术优点可以集中为： 应用本发明， 除了可以正常去除有机物等指标外， 可以使含 DMF 的合成革废水的总氮和氨 氮稳定达到 《合成革与人造革工业污染物排放标准》 （GB21902-2008 ) 制革废水氨氮、 总氮 的排放标准。
[0042] 下面结合典型试验运行情况说明本发明的方法对含二甲基甲酰胺合成革废水的处理 效果。 针对某制革公司污水厂采用本发明中的好氧污泥-厌氧填料结构的新型膜生物反应器 进行连续 3个多月的运行试验， 试验表明该新型膜生物反应器对合成革废水处理效果显著， 尤其是其中的总氮和氨氮处理效果比较稳定。 [0043] 图 1为本发明对 COD的去除效果， 从图 1 中可以看出： 启动阶段 （即： 阶段 1 ) 调 试进水 COD从 1276.2mg/L降至 210.9mg/L， 出水 COD在从 100mg/L至 158mg/L之间， 虽 然出水 COD大于 100mg/L， 但在启动阶段， 总体上 COD去除率呈下降趋势， 平均去除率仅 64.3%。 稳定运行阶段 （即： 阶段 2) (33d〜105d)， 进水 COD平均维持在 358.8mg/L， 而出 水 COD平均为 45.5mg/L， 本发明的方法对 COD的去除率平均为 72.4%， 出水 COD基本低 于 50mg/L。
[0044] 图 2 为本发明对总氮的去除效果， 虽然进水总氮的浓度波动较大， 但总出水总氮浓 度一直在稳定降低， 本发明对总氮的去除率也随之继续提高至 90%以上。 出水总氮的浓度水 平稳定低于 10mg/L， 达到了制革废水对总氮的排放标准。
[0045] 图 3 为本发明对氨氮的去除效果， 由图 3 可得知本发明的方法对氨氮去除效果明显， 稳定后出水氨氮低于 15mg/L。

Claims

权 利 要 求 书
1.一种处理含二甲基甲酰胺合成革废水的生化方法， 其步骤为：
步骤一： 将待处理的含二甲基甲酰胺合成革废水通入好氧污泥-厌氧填料结构的新型膜生物 反应器， 控制合成革废水的进水水质指标至： CODcr为 166-1276mg/L， 氨氮为 169-311 mg/L， 总氮为 203-360mg/L， 所述的好氧污泥 -厌氧填料结构的新型膜生物反应器包括好氧区和厌氧 区， 好氧区和厌氧区一体化集成或分置式设计， 两区相对封闭运行；
步骤二： 待处理的含二甲基甲酰胺合成革废水先进入好氧区， 好氧区采用专性驯化以硝化菌 为优势菌群的活性污泥， 驯化周期为 2-4 周， 控制好氧区污泥回流比为 100-300%， 并调节 好氧区的 pH值为 8-9， 好氧区的搅拌由曝气管提供， 利用好氧活性污泥实现硝化反应， 将 氨氮转化为硝酸盐氮， 并利用分离膜进行泥水分离；
步骤三： 经过好氧区处理后的合成革废水进入厌氧区， 厌氧区填充悬浮填料， 容积比为 30- 60%之间， 搅拌动力由搅拌器提供， 利用固定化厌氧生物膜进行反硝化反应， 将回流自好氧 区的合成革废水中的硝酸盐氮转化为氮气；
步骤四： 经过厌氧区处理后的合成革废水按序排出好氧污泥-厌氧填料结构的新型膜生物反 应器。
2. 根据权利要求 1 所述的一种处理含二甲基甲酰胺合成革废水的生化方法， 其特征在于： 步骤三中的悬浮填料为聚乙烯材质， 外观呈空圆柱体， 高为 7mm， 直径为 10mm， 内部有十 字支撑， 外部有翅片， 密度小于水， 空隙率达 88%， 悬浮填料总比表面积为 690 m2/m3， 供 生物膜附着的有效比表面积为 500m2/m3。
3. 根据权利要求 2 所述的一种处理含二甲基甲酰胺合成革废水的生化方法， 其特征在于： 步骤一中通入待处理的含二甲基甲酰胺合成革废水前， 好氧污泥 -厌氧填料结构的新型膜生 物反应器的初期闷曝期为 5 天， 间歇换水， COD 负荷为 0.6kg/m3 · d， 氨氮负荷为 0.2kg/m3 · d， 总氮负荷为 0.3kg/m3 · d， 10天后， 每天提高 5%的进水负荷， 运行 3个月后 稳定运行。
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