阅读说明：本技术 一种用于污水处理的活性填料及其制备方法与应用 (Active filler for sewage treatment and preparation method and application thereof ) 是由 郑展望 金鹏 徐涛 赵若瑾 李依依 于 2021-06-21 设计创作，主要内容包括：本发明提供了一种用于污水处理的活性填料及其制备方法与应用,通过使用多种材料及脱氮功能菌对填料表面进行修饰改性,使之能够达到表面粗糙、亲水亲生物及更好地处理效果,本发明使用性能优异的功能菌和海藻酸钠载体来修饰聚氨酯填料,增加聚氨酯填料的微孔结构,增大比表面积,为微生物的培养提供代谢增值的空间,长期维持微生物活性和丰度,修饰后的活性填料具有生物友好性,无环境污染,可增强微生物处理污水的能力,降低污水中的污染物含量,制备方法简单,原料来源广泛,易实现工业化生产,且制备过程不会对环境造成污染。(The invention provides an active filler for sewage treatment and a preparation method and application thereof, wherein the surface of the filler is modified by using various materials and denitrifying functional bacteria, so that the filler can achieve the effects of rough surface, hydrophily and better treatment.)

1. The active filler for sewage treatment is characterized by comprising the following raw materials in parts by weight: 4-6 parts of functional bacteria liquid, 1-2 parts of curing agent and 4-6 parts of filler carrier; wherein the functional bacteria liquid is a bacteria liquid compounded by denitrifying microorganisms.

2. The active filler for sewage treatment according to claim 1, wherein the functional bacteria liquid is one or more of pseudomonas or bacillus subtilis with high denitrification performance, and is mixed and cultured in LB culture solution to OD₆₀₀The value is in the range of 2-3, and functional bacteria liquid is obtained.

3. The active filler for sewage treatment according to claim 2, wherein the inoculation amount of the functional bacteria is 1-4%.

4. The active filler for sewage treatment according to claim 1, wherein the curing agent is prepared by mixing sodium alginate, polyvinyl alcohol and water in a ratio of 1:1:30, heating and stirring at 80-90 ℃ until completely dissolved, and cooling for later use.

5. The active filler for sewage treatment according to claim 1, wherein the filler carrier comprises a polyurethane filler or a ceramsite filler.

6. A method for preparing an active filler for sewage treatment according to any of claims 1 to 5, characterized in that it comprises the following steps:

1) fully mixing the functional bacteria liquid with a curing agent to obtain a mixed liquid;

2) immersing a filler carrier into the mixed solution obtained in the step 1);

3) immersing the filler carrier soaked in the step 2) into a crosslinking solution for crosslinking reaction, fishing out, cleaning until the filtrate is neutral, and storing for later use after air drying.

7. The preparation method of the active filler for sewage treatment according to claim 6, wherein the preparation method of the functional bacteria liquid in the step 1) comprises the following steps: inoculating two functional strains of pseudomonas and bacillus subtilis with high-efficiency denitrification performance to L respectively in the inoculation amount of 1-4%B, in a culture solution; culturing for 20-26h at 28-37 ℃ and under the conditions of 180-; further expanding and culturing the cultured bacterial liquid in a fermentation device to OD₆₀₀Is 2-3.

8. The preparation method of the active filler for sewage treatment according to claim 6, wherein the preparation method of the functional bacteria liquid in the step 1) comprises the following steps: inoculating pseudomonas into LB culture solution with the inoculum size of 1-4%; culturing for 20-26h at 28-37 ℃ and under the conditions of 180-; further expanding and culturing the cultured bacterial liquid in a fermentation device to OD₆₀₀Is 2-3.

9. The method for preparing the active filler for sewage treatment according to claim 6, wherein in the step 3), the cross-linking solution is calcium chloride cross-linking solution with a mass fraction of 3-5%, and the time of the cross-linking reaction is 6-10 h.

10. The application of the active filler for sewage treatment is characterized in that the active filler for sewage treatment is applied to the sewage treatment according to any one of claims 1 to 5, and the adding mass of the active filler for sewage treatment is 10 to 15 percent.

Technical Field

The invention belongs to the field of sewage treatment by biotechnology, relates to an active filler, and particularly relates to an active filler for sewage treatment, which can maintain high abundance and high activity of microorganisms, has a long service cycle, provides nutrient substances required by the growth and the propagation of the microorganisms, and has a simple preparation process, and a preparation method and application thereof.

Background

In the human activity area, the nitrogen circulation is seriously disturbed, so that the active nitrogen in the biosphere is increased unprecedentedly, the pollution of the nitrogen is caused, and the human and the environment are threatened. Among the problems, nitrogen-containing wastewater causes water quality deterioration and eutrophication, and the most common nitrogen-containing pollutants in underground water are ammonia nitrogen, nitrate and the like which affect the health of aquatic organisms, so that the control and elimination of the nitrogen-containing pollutants in water environmental treatment are the primary consideration. In the aspect of treating nitrogen-containing pollutants in water, a physicochemical method and a biochemical method are basically used for denitrification at home and abroad.

The physical and chemical methods comprise technologies such as air blowing, ion exchange, chemical precipitation, breakpoint chlorination and the like, but due to the defects of large investment, high operation cost, complex technical process and the like, the existing physical and chemical methods are only commonly used for treating high-concentration industrial wastewater.

The biochemical method, which realizes the removal of nitrogen through the physiological and biochemical actions of microorganisms, has great advantages over other methods, and is considered as the most economical and effective denitrification technology.

The microbial immobilization technology is a biological technology which can be repeatedly and continuously used by locating free cells in a limited space region by a chemical or physical method and maintaining the inherent activity of the free cells. In recent years, some researchers adopt a microorganism immobilization technology to fix functional bacteria to prepare bioactive fillers for treating various polluted water bodies. In the aspect of water treatment, different microorganism species can be fixed according to application requirements, so that the technology has wide application fields, can relate to biological nitrification, denitrification, phosphorus removal and the like, can be used for immobilizing screened high-efficiency strains with certain special functions according to specific requirements, and is difficult to lose microbial cells and remarkably enhanced in treatment efficiency.

In the aspect of sewage treatment, the filler is a place where microorganisms live, influences the growth, propagation, shedding and form of the microorganisms, and plays a key role in the efficiency of equipment for treating wastewater.

The problems that the filler is difficult to form a film, the film forming time is long, the formed biological film is thin, the activity is low and the like often occur in the use of the current filler.

Disclosure of Invention

The invention aims to overcome the defects of difficult film formation, long film formation time, thin biological film formation, low activity and the like of the existing filler, and provides an active filler for sewage treatment, which can achieve the effects of rough surface, hydrophile and better treatment effect by modifying the surface of the filler by using various materials and denitrification functional bacteria.

The invention also aims to provide a preparation method of the active filler for sewage treatment, which has the advantages of simple preparation method, wide raw material source, easy realization of industrial production and no environmental pollution in the preparation process.

The invention also aims to provide application of the active filler in different types of sewage treatment according to different added functional bacteria.

In order to achieve the purpose, the invention adopts the following technical scheme:

an active filler for sewage treatment comprises the following raw materials in parts by weight: 4-6 parts of functional bacteria liquid, 1-2 parts of curing agent and 4-6 parts of filler carrier; wherein the functional bacteria liquid is a bacteria liquid compounded by denitrifying microorganisms.

In the technical scheme, the filler surface is modified by using various materials and denitrification functional bacteria, so that the problems of rough surface, hydrophily and better treatment effect can be solved.

As a preferable scheme of the invention, the functional bacteria liquid is one or more of pseudomonas or bacillus subtilis with high denitrification performance, and is mixed and cultured in LB culture solution until OD is reached₆₀₀The value is in the range of 2-3, and functional bacteria liquid is obtained.

In a preferred embodiment of the present invention, the amount of the functional bacterium to be inoculated is 1 to 4%.

As a preferable scheme of the invention, the preparation method of the curing agent is to mix sodium alginate, polyvinyl alcohol and water in a ratio of 1:1:30, heat and stir at 80-90 ℃ until the mixture is completely dissolved, and cool the mixture for standby.

In a preferred embodiment of the present invention, the filler carrier comprises a polyurethane filler or a ceramsite filler.

The invention also provides a preparation method of the active filler for sewage treatment, which comprises the following steps:

1) fully mixing the functional bacteria liquid with a curing agent to obtain a mixed liquid;

2) immersing a filler carrier into the mixed solution obtained in the step 1);

3) immersing the filler carrier soaked in the step 2) into a crosslinking solution for crosslinking reaction, fishing out, cleaning until the filtrate is neutral, and storing for later use after air drying.

As a preferable scheme of the invention, the preparation method of the functional bacteria liquid in the step 1) comprises the following steps: inoculating two kinds of functional bacteria strains of pseudomonas and bacillus subtilis with high-efficiency denitrification performance into LB culture solution respectively in the inoculation amount of 1-4%;culturing for 20-26h at 28-37 ℃ and under the conditions of 180-; further expanding and culturing the cultured bacterial liquid in a fermentation device to OD₆₀₀Is 2-3.

Further, the culture medium for the enlarged culture of the fermentation tank is prepared according to the following proportion: 50kg of peptone, 25kg of yeast powder, 50kg of sodium chloride, 20kg of soybean oil and pH 7.2 in 5000L of water.

As a preferable scheme of the invention, the preparation method of the functional bacteria liquid in the step 1) comprises the following steps: inoculating pseudomonas into LB culture solution with the inoculum size of 1-4%; culturing for 20-26h at 28-37 ℃ and under the conditions of 180-; further expanding and culturing the cultured bacterial liquid in a fermentation device to OD₆₀₀Is 2-3.

Further, the culture medium for the enlarged culture of the fermentation tank is prepared according to the following proportion: 50kg of peptone, 25kg of yeast powder, 50kg of sodium chloride, 20kg of soybean oil and pH 7.2 in 5000L of water.

As a preferable scheme of the invention, in the step 3), the crosslinking solution is calcium chloride crosslinking solution with the mass fraction of 3-5%, and the time of the crosslinking reaction is 6-10 h.

The invention also provides an application of the active filler for sewage treatment, and the active filler is applied to sewage treatment, and the adding mass of the active filler for sewage treatment is 10-15%.

Compared with the prior art, the invention has the following beneficial effects:

1) the polyurethane filler is modified by using functional bacteria with excellent performance and a sodium alginate carrier, the microporous structure of the polyurethane filler is increased, the specific surface area is increased, a space for metabolism appreciation is provided for the culture of microorganisms, and the activity and abundance of the microorganisms are maintained for a long time;

2) the modified active filler has the advantages of biological friendliness and no environmental pollution, and can enhance the sewage treatment capacity of microorganisms and reduce the content of pollutants in sewage;

3) the sodium alginate can fix microorganisms in the filler, so that the loss of the microorganisms in a water body is reduced, and the load capacity of the microorganisms is increased, so that the biological biochemical characteristics are enhanced, and the sewage treatment efficiency is improved;

4) the preparation method is simple, the raw materials are wide in source, the industrial production is easy to realize, and the preparation process does not cause pollution to the environment;

5) the invention can also be applied to different types of sewage treatment according to different added functional bacteria.

Drawings

FIG. 1 is a photograph of the reactive filler prepared in example 1.

FIG. 2 is a graph showing the growth of bacterial species in the activated packing in artificial wastewater.

FIG. 3 is a graph showing the denitrification effect of the batch test of the active filler.

FIG. 4 is a graph showing the denitrification effect of the application test of the active filler.

FIG. 5 is a graph of the total nitrogen degradation effect of an application test of an active filler.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious 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.

Example 1

This example provides the preparation of an active filler:

1) pseudomonas (strain model: LT-6) is inoculated in LB culture solution with the inoculum size of 1-4%; culturing at 30 deg.C and 200r/min for 24 h; further expanding and culturing the cultured bacterial liquid in a fermentation device to OD₆₀₀2-3, wherein the culture medium for the fermentation equipment during the enlarged culture is prepared according to the following proportion: 5000L of water, 50kg of peptone, 25kg of yeast powder, 50kg of sodium chloride, 20kg of soybean oil and pH 7.2;

2) mixing sodium alginate, polyvinyl alcohol and water at a ratio of 1:1:30, heating at 80-90 deg.C, and stirring to dissolve completely to obtain solidifying agent; fully mixing a curing agent with the functional bacteria liquid obtained in the step 1) according to a mass ratio of 4:1 to obtain a mixed liquid;

3) soaking the polyurethane filler in the mixed solution obtained in the step 2); and taking out the soaked filler, crosslinking the filler in a calcium chloride crosslinking solution with the mass fraction of 4% for 8 hours, taking out the filler, washing the filler with distilled water until the filtrate is neutral, and storing the filler for later use after air drying.

As shown in figure 1, the surface of the prepared active filler is wrapped by sodium alginate, but the microstructure of the active filler still maintains pores, the specific surface area of the filler is increased, attachment points are provided for microorganisms, and required nutrients are provided for growth and propagation of the microorganisms.

Example 2

This example is the evaluation of the microbiological Properties in an active Filler

Artificial wastewater was prepared so that the initial total nitrogen concentration was 50 to 60mg/L, and the active filler of example 1 was cultured in 200mL of artificial wastewater at a volume ratio of 10%, and the growth curve was measured at 30 ℃ and 200 rpm.

As can be seen from the growth curve of the low-temperature bacteria within 72h, the OD600 value reaches the maximum value of 0.55 after 24h of culture, the exponential growth period of the strain KSND-3 is 0-24h, and the growth enters the stationary phase within 24h-48 h.

Example 3

This example is an evaluation of the mechanical Strength of the active Filler

(1) Hardness and elasticity

A texture analyzer is utilized to carry out puncture experiments on immobilized sodium alginate pseudomonas filler and blank sodium alginate filler with different concentrations (2 percent and 4 percent), the hardness and the elasticity of the immobilized sodium alginate pseudomonas filler and the blank sodium alginate pseudomonas filler are respectively measured, a P/2N probe is selected, the measuring speed is 0.5mm/s, the return speed is 0.5mm/s, the measuring depth is 3mm, and the average value of 5 parallel samples is taken as the hardness and the elasticity of the immobilized sodium alginate pseudomonas filler and the blank sodium alginate pseudomonas filler.

(2) Mechanical stability

To evaluate the mechanical stability of the active fillers, 50 each of the following 4 active fillers were prepared: filling blank sodium alginate (2%); ② sodium alginate pseudomonas filler (2%); ③ a blank sodium alginate filler (4 percent); sodium alginate pseudomonas filler (4%) is subjected to an impact test. And continuously impacting the small ball for 1h by using high-flow-rate water flow, observing the crushing condition of the small ball to judge the relative mechanical stability of the small ball, and performing 3 parallel experiments on each group. The results of the experiment are shown in table 1.

In order to investigate the physical and chemical properties of the prepared active filler, the physical and chemical properties of the active filler are studied from the aspects of apparent form, hardness, elasticity, mechanical stability and the like, and the impact resistance of the active filler in sewage is researched.

TABLE 1 results of the experiment

As can be seen from Table 1, the Pseudomonas filler prepared with a sodium alginate concentration of 4% had a good fixing effect, but the hardness was generally high. After the water flow impacts for a period of time, the number of the No. 4 fillers is 7, and the elasticity and the hardness of the unbroken fillers are measured, so that compared with the materials before an impact resistance test, the elasticity and the hardness of the unbroken fillers are reduced, but the integral structure of the unbroken fillers is still intact. This shows that the No. 4 filler can better adapt to the impact of water flow, and has stronger impact resistance and better mechanical stability.

Example 4

This example is a different batch test of activated fillers for nitrogen removal

Adding the active filler prepared in the example 1 into an erlenmeyer flask containing 200mL of artificial wastewater in an amount of 10% (v/v), carrying out shake culture at 30 ℃ and 150r/min, sampling every 12h, measuring the nitrogen content in supernatant wastewater after centrifugation, adding the cleaned filler into the newly-configured artificial wastewater after 24h, keeping the same components in each batch of wastewater, continuing the shake culture at 30 ℃ and 150r/min, and then repeating the step for each batch. This test was used to investigate the long-term effectiveness of modified fillers.

As shown in fig. 3, the test was carried out for a total of eight batches, each of which lasted 48 h. The test results are shown in the figure, in the experimental process of 8 batches, the degradation rate of ammonia nitrogen and total nitrogen of each batch reaches more than 80%, and the highest degradation rate of ammonia nitrogen is 86%. The modified carrier of the filler after the eight batches of tests is still intact except dark color, the surface of the filler has more hyphae, and the sodium alginate has no pollution to the water environment, and can be continuously used as an adsorbent and a strain carrier to be continuously applied to sewage treatment.

Example 5

The embodiment is an integrated equipment application

The active filler prepared in the example 1 is added into 5t of purification equipment for application evaluation, the adding volume ratio is 10-15%, and the water quality of inlet and outlet water of the purification equipment is detected every day. As shown in figure 4, the start-up time of the active filler is about 7-10 days, the method is faster than the traditional activated sludge method, the biofilm formation time is shortened by 30% -50%, the abundance of strains in equipment can be maintained for a long time, the maximum removal rate of total nitrogen in the sewage after stabilization can reach more than 90%, and the active filler can be continuously used for a long time and stably run after 30-day tests.

While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.