CN106745727A - A kind of denitrogenation method of acrylic fiber production process process discharge ammonia-containing water - Google Patents
A kind of denitrogenation method of acrylic fiber production process process discharge ammonia-containing water Download PDFInfo
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- CN106745727A CN106745727A CN201510801919.5A CN201510801919A CN106745727A CN 106745727 A CN106745727 A CN 106745727A CN 201510801919 A CN201510801919 A CN 201510801919A CN 106745727 A CN106745727 A CN 106745727A
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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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/341—Consortia of bacteria
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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
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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
- C02F3/307—Nitrification and denitrification treatment characterised by direct conversion of nitrite to molecular nitrogen, e.g. by using the Anammox process
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/38—Polymers
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
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Abstract
The present invention relates to a kind of denitrogenation method of acrylic fiber production process process discharge ammonia-containing water, Nitrosomas growth promoter and denitrogenation microbial inoculum are added in the biochemical treatment system of acrylic fiber production process process discharge ammonia-containing water simultaneously, start short-cut nitrification and denitrification biological denitrification process simultaneously, the Nitrosomas growth promoter includes slaine, polyamines, organic acid azanol and Na2SO3, described slaine is made up of calcium salt, mantoquita, magnesium salts and/or ferrous salt.The present invention realizes the treatment up to standard of waste water using the close denitrification microorganism of addition growth conditions with the use of Nitrosomas growth promoter, the promotion agent prescription for using is simple, the growth of denitrification microorganism can be promoted, reduce the dosage of denitrification microorganism, guarantee system maintains the denitrification ability of stabilization, and the advantage with short-cut nitrification and denitrification, further reduce cost of sewage disposal.
Description
Technical field
The invention belongs to environmental project technical field of sewage, and in particular to a kind of denitrogenation method of acrylic fiber production process process discharge ammonia-containing water.
Background technology
The larger itrogenous organic substance of a large amount of toxicity contained in waste discharge during acrylic fiber production process toxicity after each bacteroid is progressively decomposed is degraded, but end-product has ammonia nitrogen to generate, and causes acrylic fibers waste water by dry process biochemical treatment difficulty to increase.The waste water that current dry acrylic fiber process units is produced mainly is processed using anaerobic-aerobic-BAC process.Dry acrylic fiber factory sewage farm ammonia nitrogen problem in initial design considers not comprehensive enough, and design capacity of returns is smaller, it is impossible to ensures being normally carried out for nitration denitrification reaction, causes the scarce capacity of ammonia nitrogen removal.Domestic each main acrylic fiber production process factory was all once repeatedly optimized and revised for COD pollutants to former technological process, and ammonia nitrogen removal effect is not ideal enough when research shows to use Wastewater Treated by Activated Sludge Process Nitrilon waste water merely.Therefore on the basis of existing biochemical processing process how efficient removal ammonia nitrogen pollutant, be Acrylic Fibers Plant need solve problem.
In sewage disposal system, when nitrobacteria content is relatively low in activated sludge, fast-growth cannot be bred within a short period of time by environmental conditions such as regulation dissolved oxygen and pH, the sewage disposal system removal of ammonia and nitrogen for ultimately resulting in existing operation is limited in one's ability, industrially generally can solve this problem using to cultured high concentration nitrobacteria is directly delivered in sewage disposal system.Either directly cultivate nitrobacteria in sewage disposal system and nitrobacteria is still cultivated outside sewage disposal system, be required for addition to promote the material of growth, the growth rate of nitrobacteria could be accelerated.
The current research on Biostimulation agent is a lot, Chinese patent CN200510111874.5, CN200510111876.4, CN200510111877.9 and CN200510111875.X propose the nitrobacteria growth promoter using different metal salt combinations respectively, and main component includes molasses, slaine（Molysite, manganese salt, calcium salt and magnesium salts）And adsorbent.More than 20% can be improved using ammonia nitrogen removal frank after the accelerator.But because adsorbent is mainly the materials such as zeolite powder, diatomite, Powdered Activated Carbon or flyash, adding for these adsorbents will certainly increase sludge yield.Chinese patent CN201110315549.6 discloses a kind of cultural method of short-cut nitrification and denitrification granular sludge, it is characterized in that periodically adding 5-15mg/L azanols；Chinese patent CN201010168453.7 discloses a kind of method of quickly starting oxygen-poor ammonia oxidizing biofilter, it is characterized in that step（2）In add azanol, challenge inoculation sludge changes to oxygen-poor ammonia oxidizing biomembrane.Chinese patent CN201410141638.7 discloses the nutrient solution and preparation and cultural method of a kind of nitrite bacteria, its nutrient solution formula is more complicated, except being related to iron, calcium, potassium, magnesium etc. to provide the element of cell growth, the element that cobalt, molybdenum, manganese, zinc etc. promote enzymatic synthesis is further related to.
Biological reinforcing technology provides new approaches to sewage treatment area, but existing biological agent is not suitable for processing the ammonia-containing water produced during acrylic fiber production process.For the waste water produced during acrylic fiber production process, belong to the waste water that biodegradability is poor, carbon-nitrogen ratio is low, if new short-cut nitrification and denitrification technique can be used, the energy consumption of aeration process generation can be saved, the carbon source of denitrification process is saved, cost for wastewater treatment is further reduced.
The content of the invention
In order to solve the problems, such as the qualified discharge of ammonia nitrogen pollutant in Nitrilon waste water, the invention provides a kind of denitrogenation method of acrylic fiber production process process discharge ammonia-containing water.The present invention realizes the treatment up to standard of waste water using the close denitrification microorganism of addition growth conditions with the use of Nitrosomas growth promoter, the promotion agent prescription for using is simple, the growth of denitrification microorganism can be promoted, reduce the dosage of denitrification microorganism, guarantee system maintains the denitrification ability of stabilization, and the advantage with short-cut nitrification and denitrification, further reduce cost of sewage disposal.
The denitrogenation method of acrylic fiber production process process discharge ammonia-containing water of the present invention, including following content：Nitrosomas growth promoter and denitrogenation microbial inoculum are added in the biochemical treatment system of acrylic fiber production process process discharge ammonia-containing water simultaneously, start short-cut nitrification and denitrification biological denitrification process simultaneously, the Nitrosomas growth promoter includes slaine, polyamines, organic acid azanol and Na2SO3, wherein described slaine is made up of calcium salt, mantoquita, magnesium salts and/or ferrous salt.
In Nitrosomas growth promoter of the present invention, slaine is 40-100 weight portions, preferably 50-80 weight portions, polyamines are 5-30 weight portions, preferably 10-20 weight portions, and organic acid azanol is 0.05-1.5 weight portions, preferably 0.1-1.0 weight portions, Na2SO3It is 10-40 weight portions, preferably 20-30 weight portions.
In Nitrosomas growth promoter of the present invention, slaine can be calcium salt, molysite and mantoquita, wherein Ca2+、Fe2+And Cu2+Mol ratio be（5-15）:（1-8）:（0.5-5）, preferably（8-12）:（2-6）:（1-4）；Or calcium salt, magnesium salts and mantoquita, wherein Ca2+、Mg2+And Cu2+Mol ratio be（5-15）:（5-25）:（0.5-5）, preferably（8-12）:（10-20）:（1-4）；Or calcium salt, magnesium salts, molysite and mantoquita, wherein Ca2+、Mg2+、Fe2+And Cu2+Mol ratio be（5-15）:（5-25）:（1-8）:（0.5-5）, preferably（8-12）:（10-20）:（2-6）:（1-4）.
In Nitrosomas growth promoter of the present invention, calcium salt is CaSO4Or CaCl2, magnesium salts is MgSO4Or MgCl2, mantoquita is CuSO4Or CuCl2, ferrous salt is FeSO4Or FeCl2。
In Nitrosomas growth promoter of the present invention, described polyamines are the mixture of spermine, spermidine or both.The organic acid azanol is the mixture of formic acid azanol, hydroxylamine acetate or both.
In the inventive method, the dosage of Nitrosomas growth promoter is added according to promoter concentration 10-40mg/L in sewage disposal system, and preferably 20-30mg/L is added.
In the inventive method, described denitrogenation microbial inoculum can using the microbial inoculum described in CN201210130645.8, in microbial inoculum containing Staphylococcus cohnis (Staphylococcus cohnii）FSDN-C, arthrobacterium（Arthrobacter
creatinolyticus）FDN-1 and Shui Shi Flavobacteriums（Flavobacterium mizutaii）One or two in FDN-2, simultaneously containing Paracoccus denitrificans (Paracoccus
denitrificans) DN-3 and Methylobacterium (Methylobacterium phyllosphaerae) one or two in SDN-3, above-mentioned five kinds of bacterial strains are preserved in " China Committee for Culture Collection of Microorganisms's common micro-organisms center " respectively on July 14th, 2011 and on March 11st, 2010, and deposit number is respectively CGMCC NO.5062, CGMCC No.3657, CGMCC No.3659, CGMCC No.3658, CGMCC No.3660；Preservation address：Yard 1, BeiChen xi Road, Chaoyang District, Beijing City 3, above-mentioned bacterial strains are disclosed, are its Classification And Nomenclature in bracket.
In the inventive method, the dosage first of denitrogenation microbial inoculum is added according to the 0.01%-0.15% for the treatment of sewage volume per hour, is gradually successively decreased later, is successively decreased 30%-50% than the last biomass for adding every time.Sewage disposal system was unable to spoil disposal in two months after adding microbial inoculum and accelerator.For batch process reactor, it is average treatment sewage volume per hour in each process cycle that sewage volume is processed per hour.
In the inventive method, denitrogenation microbial inoculum need to coordinate Nitrosomas growth promoter to be added in batches, added every 2-5 days once, until water outlet ammonia nitrogen concentration is less than 50 mg/L, preferably shorter than 15mg/L, total nitrogen concentration is less than 50 mg/L, and preferably shorter than 25mg/L can stop adding, and system enters stable operation stage.
In the inventive method, the temperature of sewage disposal is 18-40 DEG C, and preferably 25-35 DEG C, dissolved oxygen is 0.1-5 mg/L, and preferably 0.2-2mg/L, pH is 6.5-9.0, preferably 7.5-8.5.
In the inventive method, ammonia-containing water is the waste water of generation in dry acrylic fiber production process, NH in the waste water3- N concentration is 50-400mg/L, COD（Cr methods, similarly hereinafter）Concentration is 200-500mg/L, and BOD concentration is less than 50mg/L, pH value 7.5-8.5, belongs to the waste water of biodegradability difference.
In the inventive method, the biochemical treatment system of acrylic fiber production process process discharge ammonia-containing water is the existing all active sludge processing systems being currently running, general aerobic activated sludge facture.
The processing method of acrylic fiber production process process discharge ammonia-containing water proposed by the present invention, mainly by directly adding what denitrogenation microbial inoculum coordinated Nitrosomas growth promoter to realize.The present invention adds the Nitrosomas growth promoter of special composition and proportioning in wastewater treatment process so that the microbial inoculum for being added is in slaine, polyamines, organic acid azanol and Na2SO3Collective effect under, realize fast breeding, can with fast degradation substrate, accelerate enzymatic reaction process；And stability can be improved, extend thalline service life.Denitrogenation microbial inoculum and growth promoter are used cooperatively, the impact that acrylic fiber production process process produces toxic pollutant and system in ammonia-containing water can be tolerated, it is able to maintain that the stable operation of system and can reach preferable short-cut nitrification and denitrification denitrification effect, reduces operation energy consumption and carbon source is added.
Specific embodiment
Promotion agent prescription involved by the denitrogenation method of acrylic fiber production process ammonia-containing water proposed by the present invention is simple, can accelerate growth and the propagation of denitrification microorganism, improves the activity for participating in biochemical reaction enzyme, and then improve waste water treatment efficiency；Coordinating the liquid microbial inoculum of accelerator growth has stronger tolerance and adaptability, with preferable impact resistance, intractable organic pollution can be removed while denitrogenation, realizes that acrylic fibers generate the synchronous short-cut nitrification and denitrification denitrogenation of ammonia-containing water.
The preparation method of the Nitrosomas growth promoter of embodiment 1
Nitrosomas growth promoter used in the present invention can be prepared according to CN201410585483.6, CN201410585481.7 and CN201410585655.X methods described, the method described in preferably CN201410585655.X.Ratio and formula according to the Nitrosomas growth promoter of table 1 prepare metal salt solution, using preceding by polyamines, organic acid azanol and Na2SO3It is added in metal salt solution, prepares Nitrosomas growth promoter I-III, the promoter concentration is 0.5g/L.
The formula and ratio of the Nitrosomas growth promoter of table 1
The preparation method of the microbial bacterial agent of embodiment 2
1st, thalline activation：The thalline of Staphylococcus cohnis FSDN-C activates and is with the culture medium prescription used by seed liquor culture：Beef extract：6g/L, peptone：8g/L, NaNO2：0.6g/L, methyl alcohol：0.5mL/L；The activation culture based formulas of arthrobacterium FDN-1 and Shui Shi Flavobacterium FDN-2 are：Beef extract:5g/L, peptone:10g/L, NaNO2:1g/L, adds 2.0% agar；The activation culture based formulas of Paracoccus denitrificans DN-3 are：KNO3:1g/L, sodium succinate:8g/L, KH2PO4:1g/L, FeCL2:0.5g/L, adds 2.0% agar；The activation culture based formulas of Methylobacterium SDN-3 are：Ammonium sulfate:0.5g/L, methyl alcohol:0.75mL/L, KH2PO4:1g/L, FeCL2:0.5g/L；Add 2% agar.Activated during temperature is placed on after coating uniformly on flat board for 30 DEG C of constant incubators.
2nd, it is inoculated in respectively in corresponding liquid medium with the thalline connect on collarium scraping flat board, concussion and cultivate obtains liquid bacterial agent seed liquor in 1-3 days to exponential phase under 25-35 DEG C of temperature, 150-240rpm aerobic conditions；Culture medium prescription with activation culture based formulas, without plus agar.
3rd, using above-mentioned Staphylococcus cohnis FSDN-C as No. I seed liquor, above-mentioned arthrobacterium FDN-1 and Shui Shi Flavobacteriums FDN-2 is mixed as No. II seed liquor（Thalline is according to 1:1 and 0.5:1 two kinds of ratios combine numbering II -1 and II -2 respectively）, above-mentioned Paracoccus denitrificans DN-3 and Methylobacterium SDN-3 is mixed as No. III seed liquor（Thalline is according to 1:1 and 0.5:1 two kinds of ratios combine numbering III -1 and III -2 respectively）, any group in any group in No. I seed liquor, No. II seed liquor or any one microorganism and No. III seed liquor or any one microorganism are according still further to 1:1:1 and 1:2:3 two kinds of ratio mixing are amplified culture in the reactor with good stirring system respectively, and the ammonia nitrogen concentration in nutrient solution is 200mg/L-800mg/L, carbon-nitrogen mass ratio 5：1-10：1；Condition of culture is：25 DEG C -35 DEG C of temperature, pH6.5-10.0, dissolved oxygen is less than 3.0mg/L.Collect, the liquid microbial inoculum of the different model that concentration amplification is obtained after cultivating is shown in Table 2.
Table 2 amplifies the polytypic microbial inoculum obtained after culture
Ammonia-containing water treatment of certain the acrylic fiber production process factory of embodiment 3
The waste water that certain acrylic fiber production process factory produces is by NH after SBR biochemical treatments3 -- N concentration is that 205mg/L, COD concentration are 390mg/L, and BOD concentration is less than 50mg/L, pH value 8.0.Ton water process expense is 1.2 yuan, and the sewage after treatment is unable to qualified discharge.Using the inventive method, the accelerator of embodiment 1 is added according to promoter concentration 25mg/L in sewage disposal system, simultaneously according to averagely per hour the 0.03% of handled sewage quantity to the denitrogenation microbial inoculum that embodiment 2 is added in sewage disposal system, accelerator and microbial inoculum were added once every three days, the biomass for adding successively decreases 30% than last time every time, add during accelerator and microbial inoculum, the temperature in sewage disposal system is 28 DEG C, dissolved oxygen is 0.2-2mg/L, and pH is 7.5-8.0.After operation 30 days, ton water process expense is 0.9 yuan.System water outlet ammonia nitrogen and total nitrogen concentration are shown in Table 3.
The system water outlet ammonia nitrogen of table 3 and total nitrogen concentration
From the point of view of table 3, by the treatment of 25 days, system water outlet ammonia nitrogen concentration was less than 20mg/L less than 15mg/L, total nitrogen concentration after adding accelerator and denitrogenation microbial inoculum, and waste water realizes treatment up to standard, and system enters steady operational status, and stopping adds accelerator and denitrogenation microbial inoculum.After individually adding denitrogenation microbial inoculum and individually adding accelerator, system water outlet ammonia nitrogen and total nitrogen concentration are higher, it is impossible to realize treatment up to standard.
Claims (12)
1. a kind of denitrogenation method of acrylic fiber production process process discharge ammonia-containing water, it is characterised in that including following content：Nitrosomas growth promoter and denitrogenation microbial inoculum are added in the biochemical treatment system of acrylic fiber production process process discharge ammonia-containing water simultaneously, start short-cut nitrification and denitrification biological denitrification process simultaneously, the Nitrosomas growth promoter includes slaine, polyamines, organic acid azanol and Na2SO3, described slaine is made up of calcium salt, mantoquita, magnesium salts and/or ferrous salt.
2. method according to claim 1, it is characterised in that：In described Nitrosomas growth promoter, slaine is 40-100 weight portions, and polyamines are 5-30 weight portions, and organic acid azanol is 0.05-1.5 weight portions, Na2SO3It is 10-40 weight portions.
3. method according to claim 1 and 2, it is characterised in that：In described Nitrosomas growth promoter, slaine is calcium salt, molysite and mantoquita, wherein Ca2+、Fe2+And Cu2+Mol ratio be（5-15）:（1-8）:（0.5-5）；Or calcium salt, magnesium salts and mantoquita, wherein Ca2+、Mg2+And Cu2+Mol ratio be（5-15）:（5-25）:（0.5-5）；Or calcium salt, magnesium salts, molysite and mantoquita, wherein Ca2+、Mg2+、Fe2+And Cu2+Mol ratio be（5-15）:（5-25）:（1-8）:（0.5-5）.
4. method according to claim 1, it is characterised in that：In described Nitrosomas growth promoter, calcium salt is CaSO4Or CaCl2, magnesium salts is MgSO4Or MgCl2, mantoquita is CuSO4Or CuCl2, ferrous salt is FeSO4Or FeCl2。
5. method according to claim 1, it is characterised in that：In described Nitrosomas growth promoter, polyamines are the mixture of spermine, spermidine or both；Organic acid azanol is the mixture of formic acid azanol, hydroxylamine acetate or both.
6. method according to claim 1, it is characterised in that：The dosage of Nitrosomas growth promoter is added according to promoter concentration 10-40mg/L in sewage disposal system.
7. method according to claim 1, it is characterised in that：Described denitrogenation microbial inoculum using the microbial inoculum described in CN201210130645.8, wherein containing Staphylococcus cohnis (Staphylococcus cohnii）FSDN-C, arthrobacterium（Arthrobacter creatinolyticus）FDN-1 and Shui Shi Flavobacteriums（Flavobacterium mizutaii）One or two in FDN-2, simultaneously containing Paracoccus denitrificans (Paracoccus denitrificans)
DN-3 and Methylobacterium (Methylobacterium phyllosphaerae)
One or two in SDN-3.
8. the method according to claim 1 or 7, it is characterised in that：The dosage first of denitrogenation microbial inoculum is added according to the 0.01%-0.15% for the treatment of sewage volume per hour, is gradually successively decreased later, is successively decreased 30%-50% than the last biomass for adding every time.
9. method according to claim 1, it is characterised in that：Sewage disposal system was unable to spoil disposal in two months after adding denitrogenation microbial inoculum and Nitrosomas growth promoter.
10. method according to claim 1, it is characterised in that：Denitrogenation microbial inoculum need to coordinate Nitrosomas growth promoter to be added in batches, be added every 2-5 days once, and until water outlet ammonia nitrogen concentration is less than 50mg/L, total nitrogen concentration stops adding less than 50mg/L, and system enters stable operation stage.
11. methods according to claim 1, it is characterised in that：The temperature of sewage disposal is 18-40 DEG C, and dissolved oxygen is 0.1-5mg/L, and pH is 6.5-9.0.
12. methods according to claim 1, it is characterised in that：Ammonia-containing water is the waste water of generation in dry acrylic fiber production process, NH in the waste water3- N concentration is 50-400mg/L, and COD concentration is 200-500mg/L, and BOD concentration is less than 50mg/L, pH value 7.5-8.5, belongs to the waste water of biodegradability difference.
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| US11034932B2 (en) | 2016-11-29 | 2021-06-15 | China Petroleum & Chemical Corporation | Composition capable of promoting the growth of denitrifying microorganisms and uses thereof |
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