CN106745727B - Denitrification method for ammonia-containing wastewater discharged in acrylic fiber production process - Google Patents
Denitrification method for ammonia-containing wastewater discharged in acrylic fiber production process Download PDFInfo
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Abstract
The invention relates to a denitrification method for ammonia-containing wastewater discharged in an acrylic fiber production process, which comprises the steps of simultaneously adding a nitrite growth promoter and a denitrification microbial inoculum into a biochemical treatment system for the ammonia-containing wastewater discharged in the acrylic fiber production process, and starting a simultaneous shortcut nitrification and denitrification biological denitrification process, wherein the nitrite growth promoter comprises metal salt, polyamine substances, organic acid hydroxylamine and Na2SO3The metal salt is composed of calcium salt, copper salt, magnesium salt and/or ferrous salt. The invention adopts the denitrification microorganisms with similar growth conditions to be matched with the nitrite bacteria growth promoter to realize the standard treatment of the wastewater, the formula of the used promoter is simple, the growth of the denitrification microorganisms can be promoted, the dosage of the denitrification microorganisms is reduced, the stable denitrification capability of the system is ensured, and the invention has the advantages of short-cut nitrification and denitrification and further reduces the cost of wastewater treatment.
Description
Technical Field
The invention belongs to the technical field of environmental engineering sewage treatment, and particularly relates to a denitrification method for ammonia-containing wastewater discharged in an acrylic fiber production process.
Background
A large amount of nitrogen-containing organic matters with high toxicity contained in the discharged wastewater in the production process of acrylic fibers are degraded in toxicity after being gradually decomposed by various bacteria, but ammonia nitrogen is generated in a final product, so that the biochemical treatment difficulty of the dry acrylic wastewater is increased. The waste water produced by the prior dry acrylic fiber production device is mainly treated by adopting an anaerobic-aerobic-biological activated carbon process. The ammonia nitrogen problem of the sewage treatment plant of the dry acrylic fiber factory is not considered comprehensively at the initial design, the design reflux quantity is small, the normal running of the nitrification and denitrification reaction cannot be ensured, and the ammonia nitrogen removal capability is insufficient. The prior process flow is optimized and adjusted for COD pollutants for many times by various domestic main acrylic fiber production plants, and researches show that the deaminizing and denitrogenating effects are not ideal when acrylic fiber wastewater is treated by adopting an activated sludge method. Therefore, how to remove ammonia nitrogen pollutants efficiently on the basis of the existing biochemical treatment process is a problem to be solved by the acrylon factory.
In a sewage treatment system, when the content of nitrobacteria in activated sludge is low, the nitrobacteria cannot grow and propagate quickly in a short time by adjusting the environmental conditions such as dissolved oxygen, pH and the like, and finally the ammonia nitrogen removal capability of the existing running sewage treatment system is limited. Whether the nitrifying bacteria are cultured in the sewage treatment system directly or outside the sewage treatment system, substances for promoting growth need to be added to accelerate the growth rate of the nitrifying bacteria.
At present, many researches on biological promoters are carried out, and Chinese patents CN200510111874.5, CN200510111876.4, CN200510111877.9 and CN200510111875.X respectively propose nitrifying bacteria growth promoters formed by combining different metal salts, wherein the main components comprise molasses, metal salts (iron salt, manganese salt, calcium salt and magnesium salt) and an adsorbent. The ammonia nitrogen removal rate can be improved by more than 20 percent after the accelerator is used. However, the addition of the adsorbents mainly comprises substances such as zeolite powder, diatomite, powdered activated carbon or fly ash and the like, which inevitably increases the sludge yield. Chinese patent CN201110315549.6 discloses a method for culturing short-cut nitrification and denitrification granular sludge, which is characterized in that 5-15mg/L hydroxylamine is added periodically; chinese patent CN201010168453.7 discloses a method for rapidly starting an anoxic and ammoxidation biological filter, which is characterized in that hydroxylamine is added in the step (2) to induce the inoculated sludge to be converted into an anoxic and ammoxidation biological membrane. Chinese patent CN201410141638.7 discloses a culture solution of nitrosobacteria and a preparation and culture method thereof, wherein the formula of the culture solution is complex, and the culture solution not only relates to elements for providing cell growth such as iron, calcium, potassium, magnesium and the like, but also relates to elements for promoting enzyme synthesis such as cobalt, molybdenum, manganese, zinc and the like.
The biological strengthening technology provides a new idea for the field of sewage treatment, but the existing biological agent is not suitable for treating ammonia-containing wastewater generated in the production process of acrylic fibers. Especially for the wastewater generated in the production process of acrylic fibers, the wastewater belongs to the wastewater with poor biodegradability and low carbon-nitrogen ratio, if a novel short-cut nitrification and denitrification process can be adopted, the energy consumption generated in the aeration process can be saved, the carbon source in the denitrification process can be saved, and the wastewater treatment cost can be further reduced.
Disclosure of Invention
The invention provides a denitrification method for ammonia-containing wastewater discharged in an acrylic fiber production process, aiming at solving the problem of standard discharge of ammonia-nitrogen pollutants in acrylic fiber wastewater. The invention adopts the denitrification microorganisms with similar growth conditions to be matched with the nitrite bacteria growth promoter to realize the standard treatment of the wastewater, the formula of the used promoter is simple, the growth of the denitrification microorganisms can be promoted, the dosage of the denitrification microorganisms is reduced, the stable denitrification capability of the system is ensured, and the invention has the advantages of short-cut nitrification and denitrification and further reduces the cost of wastewater treatment.
The invention relates to a denitrification method for ammonia-containing wastewater discharged in the acrylic fiber production process, which comprises the following steps: adding a nitrite growth promoter and a denitrifier into a biochemical treatment system for discharging ammonia-containing wastewater in the acrylic fiber production process at the same time, and starting a simultaneous shortcut nitrification and denitrification biological denitrification process, wherein the nitrite growth promoter comprises metal salt, polyamine substances, organic acid hydroxylamine and Na2SO3Wherein the metal salt is composed of calcium salt, copper salt, magnesium salt and/or ferrous salt.
In the nitrite bacteria growth promoter, 40-100 parts by weight of metal salt, preferably 50-80 parts by weight, 5-30 parts by weight of polyamine substance, preferably 10-20 parts by weight, 0.05-1.5 parts by weight of organic acid hydroxylamine, preferably 0.1-1.0 part by weight, Na2SO3Is 10 to 40 parts by weight, preferably 20 to 30 parts by weight.
In the nitrite bacteria growth promoter, the metal salt can be calcium salt, iron salt and copper salt, wherein Ca2+、Fe2+And Cu2+The molar ratio of (5-15): (1-8): 0.5-5, preferably (8-12): 2-6): 1-4; or calcium, magnesium and copper salts, of which Ca is present2+、Mg2+And Cu2+The molar ratio of (5-15): (5-25): 0.5-5), preferably (8-12): 10-20): 1-4; or calcium, magnesium, iron and copper salts, wherein Ca2+、Mg2+、Fe2+And Cu2+The molar ratio of (5-15): (5-25): 1-8): 0.5-5, preferably (8-12): 10-20): 2-6): 1-4.
In the nitrite bacteria growth promoter, the calcium salt is CaSO4Or CaCl2Magnesium salt is MgSO4Or MgCl2The copper salt is CuSO4Or CuCl2The ferrous salt is FeSO4Or FeCl2。
In the nitrite bacteria growth promoter, the polyamine substance is spermine, spermidine or a mixture of spermine and spermidine. The organic acid hydroxylamine is hydroxylamine formate, hydroxylamine acetate or a mixture of the two.
In the method, the addition amount of the nitrite bacteria growth promoter is added according to the concentration of the promoter in the sewage treatment system of 10-40mg/L, preferably 20-30 mg/L.
In the method of the invention, the denitrogenation microbial inoculum can adopt the microbial inoculum described in CN201210130645.8, and the microbial inoculum contains staphylococcus cohnii (S.cohnii) (A.cohnii)Staphylococcus cohnii) FSDN-C, Arthrobacter: (Arthrobacter creatinolyticus) FDN-1 and Flavobacterium aquatile (F: (F;)Flavobacterium mizutaii) One or two of FDN-2, and Paracoccus denitrificans: (Paracoccus denitrificans) DN-3 and Methylobacterium (M) ((M))Methylobacterium phyllosphaerae) One or two of SDN-3, wherein the five strains are respectively preserved in China general microbiological culture Collection center (China Committee for culture Collection of microorganisms) in 2011, 7 and 14 days and 2010, 3 and 11 days", the preservation numbers are CGMCC NO.5062, CGMCC NO.3657, CGMCC NO.3659, CGMCC NO.3658 and CGMCC NO.3660 respectively; and (4) storage address: the No.3 Hospital No. 1 Xilu, Beijing, Chaoyang, is published and named in brackets.
In the method, the first adding amount of the denitrifier is 0.01-0.15% of the volume of the sewage treated every hour, and the denitrifier is gradually decreased later, wherein the adding amount of the denitrifier is decreased by 30-50% each time compared with the last adding amount of the denitrifier. After the microbial inoculum and the accelerant are added, the sewage treatment system can not discharge sludge within two months. For a batch reactor, the hourly volume of wastewater treated is the average hourly volume of wastewater treated in each treatment cycle.
In the method, the denitrifier needs to be added with the nitrite growth promoter in batches, the denitrifier is added once every 2-5 days until the concentration of the ammonia nitrogen in the effluent is lower than 50mg/L, preferably lower than 15mg/L, the total nitrogen concentration is lower than 50mg/L, preferably lower than 25mg/L, the adding can be stopped, and the system enters a stable operation stage.
In the method of the invention, the temperature of sewage treatment is 18-40 ℃, preferably 25-35 ℃, the dissolved oxygen is 0.1-5mg/L, preferably 0.2-2mg/L, and the pH is 6.5-9.0, preferably 7.5-8.5.
In the method, the ammonia-containing wastewater is wastewater generated in the dry acrylic fiber production process, and NH in the wastewater3The N concentration is 50-400mg/L, the COD (Cr method, the same below) concentration is 200-500mg/L, the BOD concentration is less than 50mg/L, the pH value is 7.5-8.5, and the wastewater with poor biodegradability belongs to the technical field of wastewater treatment.
In the method, the biochemical treatment system for discharging ammonia-containing wastewater in the acrylic fiber production process is all the existing active sludge treatment systems in operation, and is a common aerobic active sludge treatment method.
The invention provides a method for treating ammonia-containing wastewater discharged in the acrylic fiber production process, which is mainly realized by directly adding a denitrifier and a nitrite growth promoter. In the invention, the nitrite bacteria growth promoter with special composition and proportion is added in the wastewater treatment process, so that the added microbial inoculum is prepared from metal salt, polyamine substances, organic acid hydroxylamine and Na2SO3Under the combined action ofThe rapid propagation can be realized, the substrate can be rapidly degraded, and the enzymatic reaction process is accelerated; and can improve stability and prolong the service life of the thallus. The denitrification agent and the growth promoter are matched for use, so that the impact of toxic pollutants in ammonia-containing wastewater generated in the acrylic fiber production process and a system can be resisted, the stable operation of the system can be maintained, the ideal short-cut nitrification and denitrification effect can be achieved, and the operation energy consumption and the carbon source addition are reduced.
Detailed Description
The accelerant related to the denitrification method for the ammonia-containing wastewater in the acrylic fiber production has a simple formula, can accelerate the growth and proliferation of denitrification microorganisms, improve the activity of enzymes participating in biochemical reaction, and further improve the wastewater treatment efficiency; the liquid microbial inoculum which is matched with the promoter for growth has stronger tolerance and adaptability and better impact resistance, can remove the organic pollutants which are difficult to treat while denitriding, and realizes the synchronous short-cut nitrification and denitrification denitriding of ammonia-containing wastewater generated by acrylic fibers.
EXAMPLE 1 preparation of nitrite growth promoter
The nitrite growth promoter used in the present invention may be prepared according to the methods described in CN201410585483.6, CN201410585481.7 and cn201410585655.x, preferably the methods described in cn201410585655. x. Preparing metal salt solution according to the proportion and formula of the nitrite bacteria growth promoter in the table 1, and adding polyamine substances, organic acid hydroxylamine and Na before use2SO3Adding the mixture into a metal salt solution to prepare the nitrite bacteria growth accelerant I-III, wherein the concentration of the accelerant is 0.5 g/L.
TABLE 1 formula and proportion of nitrite bacteria growth promoter
Example 2 preparation of microbial Agents
1. And (3) activation of thalli: the formula of a culture medium for activating the bacteria and culturing the seed liquid of the staphylococcus cohnii FSDN-C is as follows: beef extract: 6g/L, peptone: 8g/L, NaNO2: 0.6g/L, methanol: 0.5mL/L; the formula of the activating culture medium of arthrobacter FDN-1 and Flavobacterium aquatile FDN-2 is as follows: 5g/L beef extract, 10g/L peptone and NaNO21g/L, adding agar of 2.0 percent; the formula of the activation medium of paracoccus denitrificans DN-3 is as follows: KNO31g/L, 8g/L sodium succinate and KH2PO4:1g/L，FeCL20.5g/L, adding 2.0 percent of agar; the formula of an activation medium of methylobacterium SDN-3 is as follows: 0.5g/L ammonium sulfate, 0.75mL/L methanol, KH2PO4:1g/L，FeCL20.5 g/L; add 2% agar. After being uniformly coated on the flat plate, the flat plate is placed in a constant temperature incubator at the temperature of 30 ℃ for activation.
2. Respectively inoculating thalli scraped from the flat plate by using an inoculation ring into corresponding liquid culture solutions, and performing shake culture for 1-3 days to logarithmic phase under aerobic conditions of 25-35 ℃ and 150-240rpm to obtain liquid microbial inoculum seed solution; the formula of the culture medium is the same as that of the activation culture medium, and agar is not added.
3. Mixing the Staphylococcus cohnii FSDN-C as a No. I seed solution, the Arthrobacter FDN-1 and the Flavobacterium aquaticum FDN-2 as a No. II seed solution (thalli are combined according to two proportions of 1:1 and 0.5:1 and are respectively numbered as II-1 and II-2), the paracoccus denitrificans DN-3 and the methylobacterium SDN-3 as a No. III seed solution (thalli are combined according to two proportions of 1:1 and 0.5:1 and are respectively numbered as III-1 and III-2), mixing any group or any microorganism in the No. I seed solution and the No. II seed solution and any group or any microorganism in the No. III seed solution according to two proportions of 1:1:1 and 1:2:3, and respectively carrying out amplification culture in a reactor with a good stirring system, wherein the ammonia nitrogen concentration in the culture solution is 200mg/L-800mg/L, and the mass ratio of carbon to nitrogen is 5: 1-10: 1; the culture conditions were: the temperature is 25-35 ℃, the pH value is 6.5-10.0, and the dissolved oxygen is less than 3.0 mg/L. The liquid microbial inoculum of different types obtained after collection, concentration and amplification culture is shown in table 2.
TABLE 2 amplification of the obtained polytypic bacterial agents
EXAMPLE 3 treatment of Ammonia-containing wastewater from acrylic fiber production plant
NH of wastewater generated by certain acrylic fiber production plant after SBR biochemical treatment3 --N concentration 205mg/L, COD concentration 390mg/L, BOD concentration less than 50mg/L, pH 8.0. The cost of water treatment per ton is 1.2 yuan, and the treated sewage can not reach the discharge standard. By adopting the method, the accelerant in the embodiment 1 is added according to the concentration of the accelerant in a sewage treatment system of 25mg/L, the denitrification microbial inoculum in the embodiment 2 is added into the sewage treatment system every three days according to 0.03 percent of the average amount of sewage treated in each hour, the amount of the added bacteria is decreased by 30 percent every three days, the temperature in the sewage treatment system is 28 ℃, the dissolved oxygen is 0.2-2mg/L and the pH is 7.5-8.0 in the process of adding the accelerant and the microbial inoculum. After 30 days of operation, the cost of treatment of ton water is 0.9 yuan. The ammonia nitrogen and total nitrogen concentration of the system effluent are shown in the table 3.
TABLE 3 Ammonia nitrogen and Total Nitrogen concentrations in the effluent of the system
From the table 3, after 25 days of treatment, the ammonia nitrogen concentration of the system effluent is lower than 15mg/L and the total nitrogen concentration is lower than 20mg/L after the accelerator and the denitrification agent are added, the wastewater reaches the standard, the system enters a stable operation state, and the addition of the accelerator and the denitrification agent is stopped. After the denitrifying bacteria agent and the accelerant are added separately, the ammonia nitrogen and the total nitrogen concentration of the effluent of the system are higher, and the standard reaching treatment cannot be realized.
Claims (9)
1. A denitrification method for ammonia-containing wastewater discharged in the acrylic fiber production process is characterized by comprising the following steps: adding a nitrite growth promoter and a denitrifier into a biochemical treatment system for discharging ammonia-containing wastewater in the acrylic fiber production process at the same time, and starting a simultaneous shortcut nitrification and denitrification biological denitrification process, wherein the nitrite growth promoter comprises metal salt, polyamine substances, organic acid hydroxylamine and Na2SO3The metal salt consists of calcium salt, copper salt, magnesium salt and/or ferrous salt; in the nitrite bacteria growth promoter, the metal salt accounts for 40 to 100 weight parts5-30 parts of polyamine substance, 0.05-1.5 parts of organic acid hydroxylamine and Na2SO310-40 parts by weight; the polyamine substance is spermine, spermidine or a mixture of spermine and spermidine; the organic acid hydroxylamine is hydroxylamine formate, hydroxylamine acetate or a mixture of the two; the metal salt is calcium salt, ferrous salt and copper salt, wherein Ca2+、Fe2+And Cu2+The molar ratio of (5-15) to (1-8) to (0.5-5); or calcium, magnesium and copper salts, of which Ca is present2+、Mg2+And Cu2+The molar ratio of (5-15) to (5-25) to (0.5-5); or calcium, magnesium, ferrous and copper salts, of which Ca is present2+、Mg2+、Fe2+And Cu2+The molar ratio of (5-15): (5-25): 1-8): 0.5-5.
2. The method of claim 1, wherein: in the nitrite bacteria growth promoter, calcium salt is CaSO4Or CaCl2Magnesium salt is MgSO4Or MgCl2The copper salt is CuSO4Or CuCl2The ferrous salt is FeSO4Or FeCl2。
3. The method of claim 1, wherein: the addition amount of the nitrite bacteria growth promoter is added according to the concentration of the promoter in the sewage treatment system of 10-40 mg/L.
4. The method of claim 1, wherein: the denitrifying bacteria agent contains staphylococcus cohnii (A)Staphylococcus cohnii) FSDN-C, Arthrobacter: (Arthrobacter creatinolyticus) FDN-1 and Flavobacterium aquatile (F: (F;)Flavobacterium mizutaii) One or two of FDN-2, and Paracoccus denitrificans: (Paracoccus denitrificans) DN-3 and Methylobacterium (M) ((M))Methylobacterium phyllosphaerae) One or two of SDN-3.
5. The method according to claim 1 or 4, characterized in that: the first adding amount of the denitrifier is 0.01-0.15% of the volume of the sewage treated per hour, and the denitrifier is gradually decreased later, wherein the amount of the denitrifier added in each time is decreased by 30-50% compared with the amount of the denitrifier added in the last time.
6. The method of claim 1, wherein: after the denitrification microbial inoculum and the nitrite bacteria growth promoter are added, the sewage treatment system can not discharge sludge within two months.
7. The method of claim 1, wherein: the denitrifier is added in batches with the nitrite growth promoter, the denitrifier is added once every 2-5 days until the concentration of the ammonia nitrogen in the effluent is lower than 50mg/L and the total nitrogen concentration is lower than 50mg/L, and the system enters a stable operation stage.
8. The method of claim 1, wherein: the temperature of sewage treatment is 18-40 ℃, the dissolved oxygen is 0.1-5mg/L, and the pH is 6.5-9.0.
9. The method of claim 1, wherein: the ammonia-containing wastewater is wastewater generated in the dry acrylic fiber production process, and NH in the wastewater3The N concentration is 50-400mg/L, the COD concentration is 200-500mg/L, the BOD concentration is less than 50mg/L, the pH value is 7.5-8.5, and the wastewater with poor biodegradability belongs to the field of wastewater with poor biodegradability.
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