CN115448464A - Pharmaceutical wastewater deep denitrification method based on synchronous shortcut nitrification and denitrification process - Google Patents
Pharmaceutical wastewater deep denitrification method based on synchronous shortcut nitrification and denitrification process Download PDFInfo
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Abstract
The invention discloses a pharmaceutical wastewater deep denitrification method based on a synchronous shortcut nitrification and denitrification process, aiming at the characteristics of high nitrogen content, high organic pollutant concentration, complex components, high biotoxicity and low C/N of fermented antibiotic pharmaceutical wastewater, solving the problem of low denitrification efficiency. The method cultures SND aerobic synchronous short-cut nitrification and denitrification biological enhanced flora under aerobic condition, inoculates the SND aerobic synchronous short-cut nitrification and denitrification biological enhanced flora in a reactor containing pharmaceutical wastewater, and utilizes an organic carbon source in the wastewater to realize short-cut synchronous removal of ammonia nitrogen and nitrate nitrogen by controlling the concentration and temperature of dissolved oxygen. The synchronous shortcut nitrification and denitrification technology obtained by the method can realize synchronous shortcut nitrification and denitrification in the same reaction tank in a real sense, can fully utilize organic carbon sources in raw water, realizes synchronous and efficient removal of total nitrogen and organic matters, and provides reliable technical support for deep denitrification of the fermented antibiotic pharmaceutical wastewater.
Description
Technical Field
The invention relates to wastewater treatment, in particular to a method for deeply denitrifying pharmaceutical wastewater based on a synchronous shortcut nitrification-denitrification process, belonging to the technical field of wastewater treatment.
Background
Pharmaceutical wastewater is one of the internationally recognized serious environmental pollution sources. The high-concentration fermentation antibiotic wastewater comprises high-concentration fermentation mother liquor, extraction raffinate, solvent recovery raffinate, waste filtrate and the like discharged from a fermentation workshop, the concentration of organic pollutants is high, and the COD concentration of waste liquid such as waste acid water, waste mother liquor and the like can reach over 20000 mg/L; the nitrogen content is high, the total nitrogen can reach 700-1000 mg/L, and the nitrogen exists mainly in the forms of organic nitrogen and ammoniacal nitrogen; high chroma, high suspended matter concentration, especially the effect of antibiotic in water on inhibiting and killing microbe, high toxicity and difficult degradation of organism. In recent years, with the upgrading of the fermentation pharmaceutical technology level, the environmental control is higher and higher, and the emission requirement of total nitrogen in effluent is more severe.
Due to the toxicity of antibiotics in the pharmaceutical wastewater and the lack of carbon source in the subsequent biological treatment process, the total nitrogen removal requirement cannot be met by using the traditional biological treatment process, and the denitrification efficiency is 70-80%. When a large amount of carbon sources are added by adding carbon sources such as glucose and methanol or supplementing raw water, the discharge standard still cannot be reached, and due to the large amount of carbon sources, the excessive risk exists, the sludge yield is increased, and the operation cost is high.
The synchronous nitrification and denitrification theory is that nitrification reaction and denitrification reaction are carried out simultaneously in the same effective volume, so that aeration energy consumption and carbon source adding amount can be effectively reduced, and great application potential is realized. However, in the existing nitrification and denitrification processes, the nitrification and denitrification reactions are respectively carried out by integrating mutually independent tanks or the synchronous nitrification and denitrification are realized by realizing different dissolved oxygen concentration gradients in the same reactor, so that the water treatment process operated by the macroscopic environment theory has high energy consumption, complex process, low removal rate and unsatisfactory operation effect.
Based on the above problems, the development of the deep denitrification process of the fermented antibiotic pharmaceutical wastewater with higher efficiency and lower energy consumption is a major problem in the fermented pharmaceutical industry and is also the key for technical upgrading.
Disclosure of Invention
The invention aims to provide a method for deeply denitrifying pharmaceutical wastewater, which can really realize synchronous shortcut nitrification and denitrification in the same reaction tank, is beneficial to reducing aeration energy consumption and solving the problem of insufficient carbon source, aiming at overcoming the defects of the prior art.
The invention cultures SND (aerobic synchronous short-cut nitrification and denitrification) biological enhanced flora under aerobic condition, inoculates the SND biological enhanced flora in a reactor containing pharmaceutical wastewater, controls the concentration and temperature of dissolved oxygen in the reactor, and utilizes an organic carbon source in the wastewater to realize short-cut synchronous removal of ammonia nitrogen and nitrate nitrogen.
The invention provides a new method for the field of biological denitrification of sewage through the proposition and the deep research of a synchronous short-cut nitrification and denitrification theory, so that nitrogen can be efficiently removed under the condition of insufficient carbon source of the pharmaceutical wastewater with low carbon-nitrogen ratio. The problem that the total nitrogen of the effluent does not reach the standard in the denitrification treatment process of the pharmaceutical wastewater is fundamentally solved, and a new idea is provided for saving energy consumption.
The purpose of the invention is realized by the following technical scheme:
a pharmaceutical wastewater deep denitrification method based on a synchronous shortcut nitrification and denitrification process comprises the following steps:
1) Respectively selecting ochrobactrum, stenotrophomonas maltophilia, pseudomonas stutzeri, citrobacter freundii and paracoccus denitrificans 2 rings, transferring the two rings into a nutrient solution, independently culturing for 1-3 days at 35-37 ℃, inoculating the two rings into a proliferation culture medium according to the volume ratio of 5-15%, independently culturing for 1-3 days at 35-37 ℃, and performing centrifugal treatment (5000-8000rpm, 3-5 min) to respectively obtain cells of logarithmic growth phases of various bacteria;
2) Washing the cells in the logarithmic growth phase for 1-3 times by using a phosphate buffer solution, and then respectively mixing 18-25% of ochrobactrum anthropi, 14-18% of stenotrophomonas maltophilia, 16-20% of pseudomonas stutzeri, 20-25% of citrobacter freundii and 17-27% of paracoccus denitrificans according to the volume ratio to obtain an SND (selective non-catalytic degradation) biological enhanced flora for aerobic synchronous shortcut nitrification and denitrification;
3) Preparing the SND bioaugmentation flora into bacterial suspension with OD600 of 1.0-1.5 by using sterile water, and inoculating the bacterial suspension into a reactor containing pharmaceutical wastewater according to the proportion of 1-5%. The pharmaceutical wastewater enters the reactor after being subjected to anaerobic treatment in the anaerobic distribution tank, the concentration and the temperature of dissolved oxygen in the reactor are controlled, and the short-range synchronous removal of ammonia nitrogen and nitrate nitrogen is realized by utilizing an organic carbon source in the wastewater.
Further, the ochrobactrum, stenotrophomonas maltophilia, pseudomonas stutzeri, citrobacter freundii and paracoccus denitrificans of step 1) were purchased from the Guangdong province culture collection (cat #: GDMCC 1.1609, GDMCC 1.552, GDMCC 1.1225, GDMCC 1.1031, GDMCC 1.335).
Further, the nutrient solution in the step 1) mainly comprises the following components: 10.0g/L of tryptone, 10.0g/L of NaCl, 5.0g/L of yeast extract powder, 6.8-7.2 of pH and the balance of water.
Further, the proliferation medium in the step 1) mainly comprises the following components: 20.0g/L of casein, 3.0g/L of monopotassium phosphate, 3.0g/L of glucose, 5.0g/L of sodium chloride and the balance of water.
Further, the phosphate buffer solution in the step 2) mainly comprises the following components: 8.0g/L of sodium chloride, 7.98g/L of dipotassium phosphate trihydrate, 2.04g/L of potassium dihydrogen phosphate and the balance of water.
Further, the mass ratio of the pharmaceutical wastewater C and the pharmaceutical wastewater N entering the reactor in the step 3) is 2.0-6.0.
Further, the concentration of the dissolved oxygen in the reactor in the step 3) is controlled to be 0.5-1.5 mg/L, and the temperature is controlled to be 28-32 ℃.
Compared with the prior art, the invention has the following advantages:
1) The synchronous shortcut nitrification-denitrification technology established by the SND bio-augmentation flora can truly realize synchronous shortcut nitrification-denitrification in the same reaction tank, effectively reduce aeration energy consumption, and fully utilize raw water to avoid secondary pollution caused by overhigh sludge load;
2) The pH value is not added, the nitrification is an acid production process, the denitrification is an alkali production process, and the synchronous short-cut nitrification and denitrification technology can effectively keep the pH value in the reactor stable.
3) The construction cost of the structure is low, the nitrosation and denitrification processes are realized in the same structure, the capital construction cost is reduced, and the occupied area is saved. Effectively solves the difference of the demand of the nitrobacteria and the denitrifying bacteria on carbon source, alkalinity, sludge age and dissolved oxygen.
Drawings
FIG. 1a shows NH of the synchronous shortcut nitrification-denitrification process in example 1 4 + -N、NO 2 - -N、NO 3 - -N, TN concentration profile;
FIG. 1b shows NH of the simultaneous partial nitrification and denitrification process of example 1 4 + -N, TN removal efficiency and SND efficiency plots;
FIG. 2a shows NH of the simultaneous short-cut nitrification and denitrification process in example 2 4 + -N、NO 2 - -N、NO 3 - -N, TN concentration profile;
FIG. 2b shows NH of the simultaneous short-cut nitrification and denitrification process in example 2 4 + -N, TN removal efficiency and SND efficiency plots;
FIG. 3a shows NH of the simultaneous partial nitrification and denitrification process of example 3 4 + -N、NO 2 - -N、NO 3 - -N, TN concentration profile;
FIG. 3b shows NH in the synchronous shortcut nitrification-denitrification process in example 3 4 + N, TN removal efficiency and SND efficiency plots.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described below with reference to the following embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention discloses a pharmaceutical wastewater deep denitrification method based on a synchronous shortcut nitrification and denitrification process, aiming at the characteristics of high nitrogen content, high organic pollutant concentration, complex components, high biotoxicity and low C/N of fermented antibiotic pharmaceutical wastewater, solving the problem of low denitrification efficiency.
Example 1
1) The method comprises the following steps of respectively selecting ochrobactrum anthropi, stenotrophomonas maltophilia, pseudomonas stutzeri, citrobacter freundii and paracoccus denitrificans (all purchased from Guangdong province microbial strain preservation center, product number: GDMCC 1.1609, GDMCC 1.552, GDMCC 1.1225, GDMCC 1.1031, GDMCC 1.335) 2 loop transfer to nutrient solution (whose main components are: tryptone 10.0g/L, naCl 10.0g/L, yeast extract powder 5.0g/L, pH 7.2, balance water), cultured independently at 37 ℃ for 3 days, inoculated in a proliferation medium (the main components of which are: casein 20.0g/L, potassium dihydrogen phosphate 3.0g/L, glucose 3.0g/L, sodium chloride 5.0g/L, and water in balance), independently culturing at 37 deg.C for 3 days, centrifuging (8000rpm, 3min), and respectively obtaining cells of logarithmic growth phase of each strain;
2) The cells in the logarithmic growth phase were treated with phosphate buffer (the main components of which are: 8.0g/L of sodium chloride, 7.98g/L of dipotassium phosphate trihydrate, 2.04g/L of potassium dihydrogen phosphate and the balance of water) for 3 times, and respectively mixing 25% of ochrobactrum anthropi, 18% of stenotrophomonas maltophilia, 20% of pseudomonas stutzeri, 20% of citrobacter freundii and 17% of paracoccus denitrificans according to the volume ratio to obtain an SND biological strengthening flora for aerobic synchronous shortcut nitrification and denitrification;
3) Preparing the SND bioaugmentation flora into bacterial suspension with OD600 of 1.5 by using sterile water, and inoculating the bacterial suspension into a reactor containing pharmaceutical wastewater according to the proportion of 5%. The pharmaceutical wastewater enters a reactor after anaerobic treatment in an anaerobic distribution tank, the mass ratio of C to N is 6.0, the concentration of dissolved oxygen in the reactor is controlled to be 1.5mg/L, the temperature is controlled to be 32 ℃, and short-range synchronous removal of ammonia nitrogen and nitrate nitrogen is realized by utilizing an organic carbon source in the wastewater.
The technology of this example is adopted to denitrify the pharmaceutical wastewater (influent water quality: 392.10mg/L of ammonia nitrogen, 395.25mg/L of total nitrogen and 2371.50mg/L of COD) with a volume of 1L, and as can be seen from FIG. 1a, the effluent of the reactor only contains 27.60mg of NH 4 + -N/L，9.80mg NO 2 - -N/L，0.80mg NO 3 - -N/L,38.2mg TN/L; while NH, as shown in FIG. 1b 4 + The N removal efficiency is 92.96 percent, the TN removal efficiency is 90.34 percent, and the SND efficiency is as high as 98.37 percent.
Example 2
1) The method comprises the following steps of respectively selecting ochrobactrum anthropi, stenotrophomonas maltophilia, pseudomonas stutzeri, citrobacter freundii and paracoccus denitrificans (all purchased from Guangdong province microbial strain preservation center, product number: GDMCC 1.1609, GDMCC 1.552, GDMCC 1.1225, GDMCC 1.1031, GDMCC 1.335) 2 loop transfer to nutrient solution (whose main components are: tryptone 10.0g/L, naCl 10.0g/L, yeast extract powder 5.0g/L, pH 7.0, balance water), independently cultured at 36 ℃ for 2 days, inoculated in a proliferation medium (the main components of which are: casein 20.0g/L, potassium dihydrogen phosphate 3.0g/L, glucose 3.0g/L, sodium chloride 5.0g/L, and water in balance), independently culturing at 36 deg.C for 2 days, centrifuging (6500rpm, 4 min), and respectively obtaining cells of logarithmic growth phase of each strain;
2) The cells in the logarithmic growth phase were treated with phosphate buffer (the main components of which are: 8.0g/L of sodium chloride, 7.98g/L of dipotassium phosphate trihydrate, 2.04g/L of potassium dihydrogen phosphate and the balance of water) for 2 times, and respectively mixing 22% of ochrobactrum anthropi, 16% of stenotrophomonas maltophilia, 18% of pseudomonas stutzeri, 24% of citrobacter freundii and 20% of paracoccus denitrificans according to the volume ratio to obtain an SND biological strengthening flora for aerobic synchronous shortcut nitrification and denitrification;
3) Preparing the SND bioaugmentation flora into bacterial suspension with OD600 of 1.2 by using sterile water, and inoculating the bacterial suspension into a reactor containing pharmaceutical wastewater according to the proportion of 3%. The pharmaceutical wastewater enters a reactor after anaerobic treatment in an anaerobic distribution tank, the mass ratio of C to N is 4.0, the concentration of dissolved oxygen in the reactor is controlled to be 1.0mg/L, the temperature is controlled to be 30 ℃, and short-range synchronous removal of ammonia nitrogen and nitrate nitrogen is realized by utilizing an organic carbon source in the wastewater.
The technology of the embodiment is adopted to denitrify the pharmaceutical wastewater (the quality of the inlet water: ammonia nitrogen 649.13mg/L, total nitrogen 688.50mg/L, COD 2754.00 mg/L) with the volume of 1L, and as can be seen from figure 2a, the outlet water of the reactor only contains 31.10mg NH 4 + -N/L，14.70mg NO 2 - -N/L，3.50mg NO 3 - -N/L,49.30mg TN/L; while NH, as shown in FIG. 2b 4 + The N removal efficiency is 95.21 percent, the TN removal efficiency is 92.84 percent, and the SND efficiency is as high as 94.17 percent.
Example 3
1) The method comprises the following steps of respectively selecting ochrobactrum anthropi, stenotrophomonas maltophilia, pseudomonas stutzeri, citrobacter freundii and paracoccus denitrificans (all purchased from Guangdong province microbial strain preservation center, product number: GDMCC 1.1609, GDMCC 1.552, GDMCC 1.1225, GDMCC 1.1031, GDMCC 1.335) 2 cyclotransfer to nutrient solution (its main components are: tryptone 10.0g/L, naCl 10.0g/L, yeast extract powder 5.0g/L, pH 6.8, balance water), cultured independently at 35 ℃ for 1 day, inoculated in a proliferation medium (the main components of which are: casein 20.0g/L, potassium dihydrogen phosphate 3.0g/L, glucose 3.0g/L, sodium chloride 5.0g/L, and water in balance), independently culturing at 35 deg.C for 1 day, centrifuging (5000rpm, 5min), and respectively obtaining cells of logarithmic growth phase of each strain;
2) The cells in the logarithmic growth phase were treated with phosphate buffer (the main components of which are: 8.0g/L of sodium chloride, 7.98g/L of dipotassium phosphate trihydrate, 2.04g/L of potassium dihydrogen phosphate and the balance of water) for 1 time, respectively mixing 18 percent of ochrobactrum anthropi, 14 percent of stenotrophomonas maltophilia, 16 percent of pseudomonas stutzeri, 25 percent of citrobacter freundii and 27 percent of paracoccus denitrificans according to the volume ratio to obtain an SND biological strengthening flora for aerobic synchronous shortcut nitrification and denitrification;
3) Preparing the SND bioaugmentation flora into bacterial suspension with OD600 of 1.0 by using sterile water, and inoculating the bacterial suspension into a reactor containing pharmaceutical wastewater according to the proportion of 1%. The pharmaceutical wastewater enters a reactor after anaerobic treatment in an anaerobic distribution tank, the mass ratio of C to N is 2.0, the concentration of dissolved oxygen in the reactor is controlled to be 0.5mg/L, the temperature is controlled to be 28 ℃, and short-range synchronous removal of ammonia nitrogen and nitrate nitrogen is realized by utilizing an organic carbon source in the wastewater.
The technology of this example is adopted to denitrify the pharmaceutical wastewater (influent water quality: 481.25mg/L ammonia nitrogen, 542.11mg/L total nitrogen and 1084.00mg/L COD) with a volume of 1L, and as can be seen from FIG. 3a, the effluent of the reactor only contains 37.30mg NH 4 + -N/L，13.30mg NO 2 - -N/L，0.01mg NO 3 - -N/L,50.60mg TN/L; while NH, as shown in FIG. 3b 4 + the-N removal efficiency was 92.25%, the TN removal efficiency was 90.66%, and the SND efficiency was 88.23%.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A pharmaceutical wastewater deep denitrification method based on a synchronous shortcut nitrification and denitrification process is characterized by comprising the following steps:
1) Respectively selecting ochrobactrum, stenotrophomonas maltophilia, pseudomonas stutzeri, citrobacter freundii and paracoccus denitrificans 2 rings, transferring the rings into a nutrient solution, independently culturing, inoculating the rings into a proliferation culture medium according to the volume ratio of 5-15%, independently culturing, and centrifuging to respectively obtain cells of logarithmic phase of each bacterium;
2) Washing the cells in the logarithmic phase with a phosphate buffer solution, and mixing 18-25% of ochrobactrum anthropi, 14-18% of stenotrophomonas maltophilia, 16-20% of pseudomonas stutzeri, 20-25% of citrobacter freundii and 17-27% of paracoccus denitrificans according to the volume ratio to obtain an SND (selective non-catalytic reduction) biologically enhanced flora for aerobic synchronous shortcut nitrification and denitrification;
3) Preparing the SND bioaugmentation flora into OD by using sterile water 600 1.0-1.5 bacterial suspension, inoculating according to the proportion of 1-5%In a reactor containing pharmaceutical wastewater; the pharmaceutical wastewater enters the reactor after being subjected to anaerobic treatment in the anaerobic distribution tank, the concentration and the temperature of dissolved oxygen in the reactor are controlled, and the short-range synchronous removal of ammonia nitrogen and nitrate nitrogen is realized by utilizing an organic carbon source in the wastewater.
2. The method for deeply denitrifying pharmaceutical wastewater based on the synchronous shortcut nitrification-denitrification process of claim 1, wherein in the step 1), the ochrobactrum, stenotrophomonas maltophilia, pseudomonas stutzeri, citrobacter freundii and paracoccus denitrificans are purchased from the Guangdong province collection center of microorganism strains, and the product numbers are respectively: GDMCC 1.1609, GDMCC 1.552, GDMCC 1.1225, GDMCC 1.1031, GDMCC 1.335.
3. The method for deeply denitrifying pharmaceutical wastewater based on synchronous shortcut nitrification-denitrification process of claim 1, wherein in step 1), the culture conditions of the independent culture are as follows: independently culturing for 1-3 days at 35-37 ℃.
4. The method for deeply denitrifying pharmaceutical wastewater based on synchronous shortcut nitrification-denitrification process according to claim 1, wherein in step 1), the nutrient solution comprises the following main components: 10.0g/L tryptone, 10.0g/L NaCl, 5.0g/L yeast extract powder, 6.8-7.2 of pH and the balance of water.
5. The method for deeply denitrifying pharmaceutical wastewater based on the synchronous shortcut nitrification-denitrification process of claim 1, wherein in the step 1), the proliferation medium mainly comprises the following components: 20.0g/L of casein, 3.0g/L of monopotassium phosphate, 3.0g/L of glucose, 5.0g/L of sodium chloride and the balance of water.
6. The method for deeply denitrifying pharmaceutical wastewater based on the synchronous shortcut nitrification-denitrification process of claim 1, wherein the centrifugal treatment is performed at 5000 to 8000rpm for 3 to 5min in the step 1).
7. The method for deeply denitrifying pharmaceutical wastewater based on the synchronous shortcut nitrification-denitrification process of claim 1, wherein in the step 2), the phosphate buffer solution mainly comprises the following components: 8.0g/L of sodium chloride, 7.98g/L of dipotassium phosphate trihydrate, 2.04g/L of potassium dihydrogen phosphate and the balance of water.
8. The method for deeply denitrifying pharmaceutical wastewater based on the synchronous shortcut nitrification-denitrification process of claim 1, wherein the number of washing in step 2) is 1 to 3.
9. The method for deeply denitrifying pharmaceutical wastewater based on the synchronous shortcut nitrification-denitrification process of claim 1, wherein the mass ratio of the pharmaceutical wastewater C to N entering the reactor in the step 3) is 2.0-6.0.
10. The method for deeply denitrifying pharmaceutical wastewater based on the synchronous shortcut nitrification-denitrification process of claim 1, wherein in the step 3), the concentration of the dissolved oxygen in the reactor is controlled to be 0.5-1.5 mg/L, and the temperature is controlled to be 28-32 ℃.
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| CN117757688A (en) * | 2023-12-28 | 2024-03-26 | 中国水产科学研究院珠江水产研究所 | Citrobacter freundii JYS, and microbial inoculum and application thereof |
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2022
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117757688A (en) * | 2023-12-28 | 2024-03-26 | 中国水产科学研究院珠江水产研究所 | Citrobacter freundii JYS, and microbial inoculum and application thereof |
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