CN112375686A - Low-temperature nitrifying flora culture method suitable for tannery wastewater - Google Patents
Low-temperature nitrifying flora culture method suitable for tannery wastewater Download PDFInfo
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Abstract
The invention relates to the technical field of biological denitrification of tannery wastewater, in particular to a culture method of low-temperature nitrifying bacteria suitable for tannery wastewater, which comprises the following steps: A) standing returned sludge in a secondary sedimentation tank of a leather-making wastewater biochemical system for 1-2 hours, and removing supernatant to obtain lower-layer sludge liquid; B) freezing the lower layer sludge liquid at-20 to-30 ℃ for 5 to 10 hours, then unfreezing at 2 to 5 ℃ for 3 to 6 hours, and discarding the supernatant to obtain effective viable bacteria liquid; C) mixing the effective viable bacteria liquid, water and nutrient solution, and culturing under stirring and aeration conditions to obtain low-temperature nitrifying bacteria; in the culture process, the ammonia nitrogen concentration of the culture system is improved by adopting ammonium sulfate gradient. The culture method can reduce the ineffective bacteria of the system, thereby reducing the culture time in the later period, realizing the rapid improvement of the nitrification activity at low temperature and solving the problem that the ammonia nitrogen removal capability of the sewage treatment system is reduced at low temperature.
Description
Technical Field
The invention relates to the technical field of biological denitrification of tannery wastewater, in particular to a culture method of low-temperature nitrifying bacteria suitable for tannery wastewater.
Background
The tannery wastewater is wastewater discharged in the production process. The animal skin is usually salted or soaked in water to swell it, and then limed, fleshed and dealkalized. The water quality varies depending on the scale of the plant, the kind of hide and the tanning process. The content of ammonia nitrogen is usually very high, and can reach 1000mg/L at most. The tannery wastewater treatment method comprises the treatment of a biological filter or an activated sludge and other biochemical methods.
In the biological denitrification method of the tannery sewage, ammonia nitrogen is removed by nitrification of nitrifying bacteria in the conventional nitrification-denitrification method, novel shortcut nitrification-denitrification method and novel shortcut nitrification-anaerobic ammonia oxidation method. Nitrifying bacteria belong to the group of chemotrophic microorganisms and cannot directly utilize the free energy released by chemical reactions. The growth of the nitrifying bacteria is slow, and the generation period is 8-36 hours. The content of peptidoglycan in the cell wall of the nitrobacteria is low, and the content of protein and fat is high, so the nitrobacteria is sensitive to environmental change, and the natural nitrobacteria in the nature has poor low-temperature adaptability and tolerance ratio, and cannot take advantage of growth competition with heterotrophic microorganisms.
In winter, the content of nitrifying bacteria in the activated sludge is reduced, and the activated sludge cannot grow and propagate quickly in a short time by adjusting the environmental conditions such as dissolved oxygen, pH and the like, so that the ammonia nitrogen removal capability of the existing running sewage treatment system is reduced. Particularly in northern areas of China, the growth and reproduction rate and the biological activity of nitrifying bacteria in the activated sludge are greatly influenced, so the nitrification and deamination nitrogen effects of a plurality of sewage treatment plants are poor, and the concentration of the ammonia nitrogen in effluent water hardly meets the discharge standard.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for culturing low-temperature nitrifying bacteria suitable for tannery wastewater, which can solve the problem of the reduction of ammonia nitrogen removal capability of a sewage treatment system under a low-temperature condition.
The invention provides a method for culturing low-temperature nitrifying bacteria suitable for tannery wastewater, which comprises the following steps:
A) standing returned sludge in a secondary sedimentation tank of a leather-making wastewater biochemical system for 1-2 hours, and removing supernatant to obtain lower-layer sludge liquid;
B) freezing the lower layer sludge liquid at-20 to-30 ℃ for 5 to 10 hours, then unfreezing at 2 to 5 ℃ for 3 to 6 hours, and discarding the supernatant to obtain effective viable bacteria liquid;
C) mixing the effective viable bacteria liquid and the nutrient solution, and culturing under the conditions of stirring and aeration to obtain low-temperature nitrifying bacteria;
in the culture process, the ammonia nitrogen concentration of the culture system is improved by adopting ammonium sulfate gradient.
Preferably, NaHCO is contained in the return sludge of the secondary sedimentation tank3The content of (A) is 1.3-2.6 g/L, K2HPO4The content of (A) is 1.0-1.3 g/L, the content of NaCl is 0.2-0.3 g/L, FeSO4The content of (b) is 0.03-0.05 g/L, MgSO4The content of (1) is 0.03-0.05 g/L, CaCl2The content of (b) is 0.1-0.2 g/L, and the content of glucose is 0.04-0.06 g/L.
Preferably, the nitrification activity of the return sludge of the secondary sedimentation tank of the leather-making wastewater biochemical system at 20-30 ℃ is 50-100 mg/(L.d).
Preferably, in the step C), the volume of the nutrient solution accounts for 60-100% of the volume of the returned sludge of the secondary sedimentation tank.
Preferably, in step C), NaHCO is added to the nutrient solution3The content of (A) is 1.3-2.6 g/L, K2HPO4The content of (A) is 1.0-1.3 g/L, NaClFeSO with a content of 0.2-0.3 g/L4The content of (b) is 0.03-0.05 g/L, MgSO4The content of (1) is 0.03-0.05 g/L, CaCl2The content of (b) is 0.1-0.2 g/L, and the content of glucose is 0.04-0.06 g/L.
Preferably, in step C), the culture conditions include:
the pH value is 7.0-8.0, the temperature is 5-8 ℃, and the DO is 1.0-1.5 mg/L.
Preferably, in the step C), ammonium sulfate is adopted to control the initial ammonia nitrogen concentration of the culture to be 40-50 mg/L.
Preferably, in the step C), 5-7 days are taken as one culture period for the culture, and 6-8 culture periods are cultured together.
Preferably, in the step C), the gradient of the increase of the ammonia nitrogen concentration of the culture system is controlled to be 10-20 mg/L each time.
The invention provides a method for culturing low-temperature nitrifying bacteria suitable for tannery wastewater, which comprises the following steps: A) standing returned sludge in a secondary sedimentation tank of a leather-making wastewater biochemical system for 1-2 hours, and removing supernatant to obtain lower-layer sludge liquid; B) freezing the lower layer sludge liquid at-20 to-30 ℃ for 5 to 10 hours, then unfreezing at 2 to 5 ℃ for 3 to 6 hours, and discarding the supernatant to obtain effective viable bacteria liquid; C) mixing the effective viable bacteria liquid and the nutrient solution, and culturing under the conditions of stirring and aeration to obtain low-temperature nitrifying bacteria; in the culture process, the ammonia nitrogen concentration of the culture system is improved by adopting ammonium sulfate gradient. The method for culturing the low-temperature nitrifying bacteria colony suitable for the tannery wastewater can change the content of effective nitrifying bacteria in the original bacteria colony and reduce ineffective bacteria of the system, thereby reducing the culture time in the later period, realizing the rapid improvement of the nitrification activity at low temperature and solving the problem of the reduction of the ammonia nitrogen removal capability of a sewage treatment system under the low-temperature condition.
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FIG. 1 shows the ammonia nitrogen index of the effluent of a biochemical system before and after adding a low-temperature nitrifying bacteria group into an aerobic tank in example 2 of the present invention;
FIG. 2 shows the ammonia nitrogen index of the effluent of the biochemical system before and after adding the low-temperature nitrifying bacteria in the aerobic tank in embodiment 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for culturing low-temperature nitrifying bacteria suitable for tannery wastewater, which comprises the following steps:
A) standing returned sludge in a secondary sedimentation tank of a leather-making wastewater biochemical system for 1-2 hours, and removing supernatant to obtain lower-layer sludge liquid;
B) freezing the lower layer sludge liquid at-20 to-30 ℃ for 5 to 10 hours, then unfreezing at 2 to 5 ℃ for 3 to 6 hours, and discarding the supernatant to obtain effective viable bacteria liquid;
C) mixing the effective viable bacteria liquid and the nutrient solution, and culturing under the conditions of stirring and aeration to obtain low-temperature nitrifying bacteria;
in the culture process, the ammonia nitrogen concentration of the culture system is improved by adopting ammonium sulfate gradient.
According to the invention, firstly, the return sludge of the secondary sedimentation tank of the leather-making wastewater biochemical system is taken and kept stand for 1-2 h, and then the supernatant is discarded to obtain the lower layer sludge liquid.
In some embodiments of the invention, the secondary sedimentation tank returns sludge, NaHCO3The content of (A) is 1.3-2.6 g/L, K2HPO4The content of (A) is 1.0-1.3 g/L, the content of NaCl is 0.2-0.3 g/L, FeSO4The content of (b) is 0.03-0.05 g/L, MgSO4The content of (1) is 0.03-0.05 g/L, CaCl2The content of (b) is 0.1-0.2 g/L, and the content of glucose is 0.04-0.06 g/L.
The invention adopts the return sludge of a secondary sedimentation tank of a leather-making wastewater biochemical system as the initial nitrifying bacteria group. In some embodiments of the invention, the nitrification activity (ammonia nitrogen degradation rate) of the return sludge of the secondary sedimentation tank of the leather-making wastewater biochemical system at 20-30 ℃ is 50-100 mg/(L.d).
In certain embodiments of the invention, the volume of return sludge in the secondary sedimentation tank is 100L.
In certain embodiments of the invention, the time of standing is 1.5 hours.
In certain embodiments of the invention, the volume of the portion of the supernatant is 60% of the volume of the total supernatant.
After the returned sludge is kept stand for 1-2 hours, and the supernatant is discarded, the content of harmful substances in the original returned sludge can be reduced. The obtained lower layer sludge liquid contains flora.
And after the lower layer sludge liquid is obtained, freezing the lower layer sludge liquid at-20 to-30 ℃ for 5 to 10 hours, then unfreezing at 2 to 5 ℃ for 3 to 6 hours, and discarding the supernatant to obtain the effective viable bacteria liquid.
And (3) freezing the lower-layer sludge liquid at the temperature of-20 to-30 ℃ for 5 to 10 hours, so that the composition of the flora can be changed, the mixed bacteria can be reduced, the proportion of low-temperature resistant nitrifying bacteria can be improved, and the low-temperature resistance of the nitrifying bacteria agent can be enhanced. In certain embodiments of the invention, the temperature at which the lower layer sludge liquor is frozen is-25 ℃. In certain embodiments of the invention, the time for freezing the lower layer sludge liquid is 8 hours.
Unfreezing at 2-5 ℃ for 3-6 h, and removing the supernatant to remove ineffective bacteria and nutrient substances and keep effective viable bacteria. In certain embodiments of the invention, the thawing temperature is 3 ℃. In certain embodiments of the invention, the thawing time is 4 hours.
The lower-layer sludge liquid is frozen for 5-10 hours at the temperature of-20 to-30 ℃ and then unfrozen for 3-6 hours at the temperature of 2-5 ℃, so that the content of effective nitrobacteria in the original flora can be changed, and ineffective bacteria of the system can be reduced, so that the later culture time is shortened, and the nitrification activity at low temperature is rapidly improved.
After the effective viable bacteria liquid is obtained, mixing the effective viable bacteria liquid, water and nutrient solution, and culturing under the conditions of stirring and aeration to obtain low-temperature nitrifying bacteria;
in the culture process, the ammonia nitrogen concentration of the culture system is improved by adopting ammonium sulfate gradient.
In certain embodiments of the invention, the volume of the nutrient solution is 60% to 100% of the volume of the return sludge of the secondary sedimentation tank. In certain embodiments, the volume of the nutrient solution is 60% of the volume of the return sludge of the secondary sedimentation tank.
In certain embodiments of the invention, the solvent in the nutrient solution is water.
In certain embodiments of the invention, the nutrient solution comprises NaHCO3、K2HPO4、NaCl、FeSO4、MgSO4、CaCl2Glucose and water.
In certain embodiments of the invention, the nutrient solution is NaHCO3The content of (A) is 1.3-2.6 g/L, K2HPO4The content of (A) is 1.0-1.3 g/L, the content of NaCl is 0.2-0.3 g/L, FeSO4The content of (b) is 0.03-0.05 g/L, MgSO4The content of (1) is 0.03-0.05 g/L, CaCl2The content of (b) is 0.1-0.2 g/L, and the content of glucose is 0.04-0.06 g/L.
In certain embodiments of the invention, the conditions of the culturing include:
the pH value is 7.0-8.0, the temperature is 5-8 ℃, and the DO is 1.0-1.5 mg/L.
In certain embodiments, the pH of the culture is 7.0. In certain embodiments, the temperature of the incubation is 6 ℃.
The stirring and aerating method is not particularly limited, and DO of the solution can be 1.0-1.5 mg/L.
The method further performs domestication culture at the temperature of 5-8 ℃, greatly enhances the adaptability of the microbial inoculum at low temperature, and can quickly improve the nitrification activity of the microbial inoculum.
In some embodiments of the invention, ammonium sulfate is used to control the initial ammonia nitrogen concentration of the culture to be 40-50 mg/L.
In some embodiments of the present invention, the culturing takes 5-7 days as one culturing period, and the culturing lasts for 6-8 culturing periods. In certain embodiments, the culturing is performed for 6 culturing cycles, with 7d as one culturing cycle.
In some embodiments of the invention, the concentration of ammonia nitrogen in the culture system is increased within a range of 10-20 mg/L in each culture period. In certain embodiments, the elevated concentration of ammonia nitrogen concentration in the culture system is in the range of 15mg/L per culture cycle.
The low-temperature nitrifying bacteria after culture can be cultured for 5-6 weeks at the low temperature of 5-8 ℃, the nitrifying activity of the obtained low-temperature nitrifying bacteria is 100-120 mg/(L.d), and the problem that the normal-temperature high-efficiency nitrifying bacteria lose activity at the low temperature is solved.
The low-temperature nitrifying flora cultured by the method has high ammonia nitrogen oxidation activity at low temperature, can form low-temperature short-cut nitrification-denitrification together with a denitrifying microbial agent, reduces ammonia nitrogen, solves the problem of total nitrogen and saves the overall treatment cost in winter.
The method for culturing the low-temperature nitrifying bacteria colony suitable for the tannery wastewater can change the content of effective nitrifying bacteria in the original bacteria colony and reduce ineffective bacteria of the system, thereby reducing the culture time in the later period, realizing the rapid improvement of the nitrification activity at low temperature and solving the problem of the reduction of the ammonia nitrogen removal capability of a sewage treatment system under the low-temperature condition.
In order to further illustrate the present invention, the method for culturing low temperature nitrifying bacteria suitable for tannery wastewater provided by the present invention is described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Adopting secondary sedimentation tank backflow sludge of Shandong Xintianhong leather sewage treatment plant, wherein the nitrification activity of the secondary sedimentation tank backflow sludge at 20-30 ℃ is 50-100 mg/(L.d);
refluxing 100L of sludge by using the secondary sedimentation tank, standing for 1.5h, and removing supernatant to obtain lower-layer sludge liquid;
freezing the lower layer sludge liquid at-25 deg.C for 8h, taking out, thawing at 3 deg.C for 4h, removing supernatant, and supplementing 60L nutrient solution; the nutrient solution comprises the following components in percentage by weight: NaCl content of 0.2-0.3 g/L, FeSO4The content of (b) is 0.03-0.05 g/L, MgSO4The content of (1) is 0.03-0.05 g/L, CaCl20.1-0.2 g/L of glucose, 0.04-0.06 g/L of glucose, and water;
culturing in a 150L culture tank under the conditions of stirring and aeration, adjusting the pH value to 7.0, controlling the initial ammonia nitrogen concentration to be 45mg/L and the DO to be 1.0-1.5 by ammonium sulfate, and culturing at the low temperature of 6 ℃ for 6 weeks (the ammonia nitrogen concentration of a culture system is increased by 15mg/L every week) to obtain the low-temperature nitrifying flora, wherein the highest nitrifying activity can reach 113 mg/(L.d).
Example 2
The daily treatment capacity of a sewage treatment plant of a certain leather company is 200-300 m3The water quality index is unstable, the COD of the inlet water is 700-1700 mg/L, and the ammonia nitrogen content is 350-1000 mg/L. The biochemical system adopts an A2O process, and after subsequent flocculation treatment, the COD of the discharged water is required to be less than or equal to 300mg/L, and the ammonia nitrogen content is required to be less than or equal to 70 mg/L. The lowest temperature of the biochemical system reaches 8 ℃ in winter, the ammonia nitrogen effluent index of the aerobic tank is unstable, and the effluent is more than 70mg/L within 6 days.
Adding the low-temperature nitrifying bacteria colony prepared in the embodiment 1 into the aerobic pool, wherein the volume of the low-temperature nitrifying bacteria colony accounts for 0.1% of the volume of sewage in the aerobic pool, controlling the water inflow to be 30% of the normal water inflow, and supplementing nutrient salts with the same volume concentration as that of the low-temperature nitrifying bacteria colony, wherein the nutrient salt comprises the following components: NaCl content of 0.2-0.3 g/L, FeSO4The content of (b) is 0.03-0.05 g/L, MgSO4The content of (1) is 0.03-0.05 g/L, CaCl20.1-0.2 g/L, 0.04-0.06 g/L glucose, and water. By using Na2CO3The pH of the aqueous solution (concentration is 50-80 g/L) is controlled to be 7.0-8.0. Adjusting aeration quantity, strictly controlling DO between 1.0-1.5, and allowing the low-temperature nitrifying bacteria to adapt and propagate in the system for 24 hours. And after 24 hours, normal water inflow is recovered, the pH is continuously and strictly controlled to be 7.0, the DO is controlled to be 1.0-1.5, and the temperature is 5-10 ℃.
After the low-temperature nitrifying bacteria are added into the biochemical aerobic tank, after an adaptation period of 2-3 d, the ammonia nitrogen in the effluent begins to decrease under the condition of an ambient temperature of 5-10 ℃. And after 3d, normal water inlet is recovered, the ammonia nitrogen index of the outlet water is continuously and stably reduced, the later-stage outlet water stably reaches the standard, and the lowest outlet water reaches 8.0 mg/L.
FIG. 1 shows the ammonia nitrogen index of the effluent of the biochemical system before and after adding the low-temperature nitrifying bacteria in the aerobic tank in example 2 of the present invention.
Example 3
Daily treatment capacity 1700m of sewage treatment plant of certain leather company3The water quality index is unstable, the COD of the inlet water is 700-1100 mg/L, and the ammonia nitrogen content is 220-350 mg/L. The biochemical system is the same as the A2O process, and the drainage requires COD less than or equal to 300mg/L and ammonia nitrogen content less than or equal to 70 mg/L. The temperature of the biochemical system in winter is as low as 14.0 ℃, the ammonia nitrogen effluent index of the aerobic tank is unstable, and the effluent is more than 70mg/L within 30 days and 8 days.
Adding the low-temperature nitrifying bacteria colony prepared in the embodiment 1 into the aerobic pool, wherein the volume of the low-temperature nitrifying bacteria colony accounts for 0.05 percent of the volume of sewage in the aerobic pool, controlling the water inflow to be 30 percent of the normal water inflow, supplementing nutrient salt with the same volume concentration as that of the low-temperature nitrifying bacteria colony, and the nutrient salt comprises the following components: NaCl content of 0.2-0.3 g/L, FeSO4The content of (b) is 0.03-0.05 g/L, MgSO4The content of (1) is 0.03-0.05 g/L, CaCl20.1-0.2 g/L, 0.04-0.06 g/L glucose, and water. By using Na2CO3The pH of the aqueous solution (concentration is 50-80 g/L) is controlled to be 7.5-8.0. Adjusting aeration quantity, strictly controlling DO between 1.0-1.5, and allowing the low-temperature nitrifying bacteria to adapt and propagate in the system for 24 hours. And after 24 hours, normal water inflow is recovered, the pH is continuously and strictly controlled to be 7.0, the DO is controlled to be 1.0-1.5, and the temperature is 10-15 ℃.
After the low-temperature nitrifying bacteria agent is added into the biochemical aerobic tank, after an adaptation period of 2-3 d, the ammonia nitrogen in the effluent begins to decrease under the condition of the environmental temperature of 10-15 ℃. Normal water inlet is recovered after the microbial inoculum is supplemented for 3d, the index of the ammonia nitrogen in the outlet water is continuously and stably reduced, the later-stage outlet water stably reaches the standard, and the lowest outlet water ammonia nitrogen reaches 2.1 mg/L.
FIG. 2 shows the ammonia nitrogen index of the effluent of the biochemical system before and after adding the low-temperature nitrifying bacteria in the aerobic tank in embodiment 3 of the present invention.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A method for culturing low-temperature nitrifying bacteria suitable for tannery wastewater comprises the following steps:
A) standing returned sludge in a secondary sedimentation tank of a leather-making wastewater biochemical system for 1-2 hours, and removing supernatant to obtain lower-layer sludge liquid;
B) freezing the lower layer sludge liquid at-20 to-30 ℃ for 5 to 10 hours, then unfreezing at 2 to 5 ℃ for 3 to 6 hours, and discarding the supernatant to obtain effective viable bacteria liquid;
C) mixing the effective viable bacteria liquid and the nutrient solution, and culturing under the conditions of stirring and aeration to obtain low-temperature nitrifying bacteria;
in the culture process, the ammonia nitrogen concentration of the culture system is improved by adopting ammonium sulfate gradient.
2. The culture method according to claim 1, wherein NaHCO is contained in the return sludge of the secondary sedimentation tank3The content of (A) is 1.3-2.6 g/L, K2HPO4The content of (A) is 1.0-1.3 g/L, the content of NaCl is 0.2-0.3 g/L, FeSO4The content of (b) is 0.03-0.05 g/L, MgSO4The content of (1) is 0.03-0.05 g/L, CaCl2The content of (b) is 0.1-0.2 g/L, and the content of glucose is 0.04-0.06 g/L.
3. The culture method according to claim 1, wherein the nitrification activity of the return sludge of the secondary sedimentation tank of the tannery wastewater biochemical system at 20-30 ℃ is 50-100 mg/(L.d).
4. The culture method according to claim 1, wherein in the step C), the volume of the nutrient solution accounts for 60-100% of the volume of the return sludge of the secondary sedimentation tank.
5. The method according to claim 1, wherein the culture medium is,characterized in that in the step C), NaHCO is added into the nutrient solution3The content of (A) is 1.3-2.6 g/L, K2HPO4The content of (A) is 1.0-1.3 g/L, the content of NaCl is 0.2-0.3 g/L, FeSO4The content of (b) is 0.03-0.05 g/L, MgSO4The content of (1) is 0.03-0.05 g/L, CaCl2The content of (b) is 0.1-0.2 g/L, and the content of glucose is 0.04-0.06 g/L.
6. The method according to claim 1, wherein in step C), the culture conditions comprise:
the pH value is 7.0-8.0, the temperature is 5-8 ℃, and the DO is 1.0-1.5 mg/L.
7. The culture method according to claim 1, wherein in the step C), ammonium sulfate is used for controlling the initial ammonia nitrogen concentration of the culture to be 40-50 mg/L.
8. The culture method according to claim 1, wherein in step C), the culture is performed for 5-7 d for one culture period, and the culture is performed for 6-8 culture periods.
9. The culture method according to claim 1, wherein in the step C), the gradient of the increase of the ammonia nitrogen concentration of the culture system is controlled to be 10-20 mg/L each time.
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US20020177119A1 (en) * | 2001-05-22 | 2002-11-28 | Richard Wisniewski | Cryopreservation system with controlled dendritic freezing front velocity |
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US20020177119A1 (en) * | 2001-05-22 | 2002-11-28 | Richard Wisniewski | Cryopreservation system with controlled dendritic freezing front velocity |
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张雷等: "耐低温硝化细菌固定化技术及脱氮效果", 《化工进展》 * |
盛晓琳等: "低温硝化活性污泥的富集及其生物强化效果", 《净水技术》 * |
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