CN117263403B - Sewage treatment agent based on denitrifying bacteria and preparation method thereof - Google Patents
Sewage treatment agent based on denitrifying bacteria and preparation method thereof Download PDFInfo
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Classifications
-
- 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
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
-
- 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
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
-
- 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
-
- 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
- C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biological Treatment Of Waste Water (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention provides a sewage treatment agent based on denitrifying bacteria and a preparation method thereof, and the method for preparing the sewage treatment agent based on denitrifying bacteria comprises the following steps: s10: adding carbon source particles into a silane coupling agent aqueous solution, and coupling to obtain a silanized carbon source material; s20: adding the silanized carbon source particles into denitrifying bacteria bacterial liquid, and uniformly mixing to obtain a first mixed liquid; s30: adding polyvinyl alcohol, sodium alginate and cellulose into water, and uniformly mixing to obtain a second mixed solution; s40: uniformly mixing the first mixed solution and the second mixed solution, then dripping the mixed solution into the first crosslinking solution, and curing and crosslinking to obtain gel microspheres; s50: and adding the gel microspheres into a second crosslinking solution, and further crosslinking to obtain the sewage treatment agent. The sewage treatment agent obtained by the method can effectively promote denitrification reaction, improve denitrification effect and reduce total nitrogen content in sewage.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a sewage treatment agent based on denitrifying bacteria and a preparation method thereof.
Background
Nitrogen is an important factor for eutrophication of water, and is necessary to improve the denitrification efficiency of sewage treatment plants, and can relieve the current situation of eutrophication of water.
The nitrification-denitrification is the most effective and economical denitrification technology of the sewage treatment plant, total nitrogen is one of the most main indexes in the tail water discharged by the sewage treatment plant, the total nitrogen content is not easy to reach the national standard, the problem to be solved by each sewage treatment plant is always the problem to be solved, and meanwhile, more and more sewage plants start to search for a method capable of deeply denitrifying due to higher and higher requirements on denitrification. However, nitrification is relatively easy to achieve as long as sufficient dissolved oxygen and a sufficiently long sludge residence time are provided for nitrification. However, denitrification is difficult to achieve because it requires a sufficient electron donor, so nitrate is the major component of total nitrogen in most cases. In order to effectively reduce the concentration of nitrate, a sufficient carbon source needs to be ensured in the denitrification water treatment process so as to promote the denitrification reaction, thereby achieving the purpose of reducing the concentration of nitrate. Most of the current sewage treatment technologies have to increase the cost and increase the consumption of carbon sources in order to reach the total nitrogen emission standard. However, the cost of adding the carbon source for sewage treatment is relatively high, and in addition, the carbon source is not only utilized by denitrifying bacteria, but also competes with other strains in the sewage treatment process, so that the consumption of the carbon source is definitely further increased.
Aiming at the problems, the patent CN110668561A discloses an organic composite powder carrier and application thereof in urban sewage treatment enhanced biological denitrification, wherein the organic composite powder carrier is formed by compositing a microorganism carrier with larger equivalent particle size and superfine powdery organic substitute carbon source, and the organic substitute carbon source is short-chain-polyhydroxyalkanoate superfine powder which can be selectively utilized by nitrifying and denitrifying microorganisms. In the invention, the polyhydroxyalkanoate material is not easy to be degraded by common biological bacteria or used as a nutrition source, but can be used by denitrifying bacteria as an electron donor for denitrification, and the microbial carrier provides adsorption sites of the denitrifying bacteria so as to promote the continuous progress of denitrification reaction. However, there is a problem in that other bacteria which can utilize polyhydroxyalkanoate-like materials may exist in the sewage as well, and the effect of promoting the denitrification reaction is limited only by optimizing the kind of the carbon source.
It is therefore desirable to provide a sewage treatment agent having a good denitrification effect.
Disclosure of Invention
The invention provides a sewage treatment agent based on denitrifying bacteria and a preparation method thereof, and the sewage treatment agent can effectively reduce the content of nitrogen-oxygen compounds in sewage, thereby reducing the total nitrogen content of the sewage.
In a first aspect, the present invention provides a method for preparing a denitrifying bacteria-based sewage treatment agent, comprising the steps of:
s10: adding carbon source particles into a silane coupling agent KH550 aqueous solution, and coupling to obtain silanized carbon source particles, wherein the carbon source particles comprise at least one of alkali modified corncob particles and alkali modified wheat straw particles;
s20: adding the silanized carbon source particles into denitrifying bacteria bacterial liquid, and uniformly mixing to obtain a first mixed liquid;
s30: adding polyvinyl alcohol, sodium alginate and cellulose into water, and uniformly mixing to obtain a second mixed solution;
s40: uniformly mixing the first mixed solution and the second mixed solution, then dripping the mixed solution into the first crosslinking solution, and curing and crosslinking to obtain gel microspheres;
s50: and adding the gel microspheres into a second crosslinking solution, and further crosslinking to obtain the sewage treatment agent.
According to the method, denitrifying bacteria are combined with carbon source particles, polyvinyl alcohol and sodium alginate are used for embedding the carbon source particles combined with the denitrifying bacteria and cellulase, the sewage treatment agent is obtained after two times of crosslinking, the carbon source particles in the sewage treatment agent can be directly utilized by the denitrifying bacteria, meanwhile, the cellulase can also promote the utilization of the denitrifying bacteria to the carbon source particles, and in addition, the polyvinyl alcohol and sodium alginate gel subjected to secondary crosslinking can slow down the outward permeation of decomposition products of the carbon source particles, so that most of carbon sources in the sewage treatment agent are utilized by the denitrifying bacteria, the denitrification reaction is promoted, the denitrification effect is improved, and the total nitrogen content in sewage is reduced.
In some embodiments, in the step S10, the dosage ratio of the carbon source particles to the aqueous solution of the silane coupling agent KH550 is 1g: 10-50 mL, wherein the mass percentage of the aqueous solution of the silane coupling agent KH550 is 1-5%.
In some embodiments, in the step S20, the usage ratio of the silanized carbon source particles to the denitrifying bacteria bacterial liquid is 1g: 5-50 mL, and the OD600 of the denitrifying bacteria bacterial liquid is 0.8-1.2.
In some embodiments, in the step S30, the dosage ratio of the polyvinyl alcohol, sodium alginate and water is 10g: 1-5 g: 20-100 mL, wherein the concentration of the cellulase in the second mixed solution is 10-200U/mL.
In some embodiments, in the step S40, the usage ratio of the first mixed solution to the second mixed solution is 1: 5-10.
In some embodiments, in the step S40, the first crosslinking solution is a saturated boric acid solution including 2-5 wt% of calcium chloride.
In some embodiments, in the step S50, the second crosslinking solution is a saturated boric acid solution including 0.5-2 wt% glutaraldehyde and 2-5 wt% calcium chloride.
In a second aspect, the application provides a sewage treatment agent based on denitrifying bacteria, which is prepared by the method according to any embodiment of the first aspect.
In a third aspect, the present application provides a method for wastewater treatment comprising: adding the sewage treatment agent prepared by the method according to any one of the first aspect or the sewage treatment agent according to any one of the second aspect into sewage, and performing denitrification treatment to obtain treated sewage.
Detailed Description
Each example or embodiment in this specification is described in a progressive manner, each example focusing on differences from other examples.
In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
As described in the background art, in the course of nitrogen-containing sewage treatment, denitrification is one of the main factors limiting the decrease in total nitrogen content in sewage, and thus it is required to provide a sewage treatment agent having a good denitrification effect.
General biological denitrification NO is produced by denitrifying bacteria 3 - As electron acceptors, they are finally reduced to N by a series of reduction products 2 Is a process of (2). Biological denitrification includes autotrophic denitrification and heterotrophic denitrification. The autotrophic denitrification process is to take hydrogen or elemental sulfur as electron donor by autotrophic denitrifying bacteria under anaerobic condition, and NO 3 - Reduction to N 2 Is a process of (2). Autotrophic denitrification has the advantages of no need of additional carbon source, less sludge production, low denitrification rate and SO (effluent) 4 2- And the concentration exceeds the standard. Heterotrophic denitrification is a heterotrophic bacterium with denitrification function, which uses organic carbon as electron donor to complete NO 3 - Reduction to N 2 Heterotrophic denitrifying bacteria have higher denitrification efficiency and are widely used in actual sewage treatment, however, in the denitrification treatment of sewage with low carbon-nitrogen ratio (carbon-nitrogen ratio is less than 5), the denitrification effect is poor due to insufficient carbon source, so that additional carbon source is required to maintain the normal operation of the denitrification process.
The problem of adding additional carbon sources is that the content of microorganisms in the sewage is generally high, and the added carbon sources are often partially not utilized by denitrifying bacteria to promote denitrification reaction, but are utilized by other microorganisms, and particularly when the denitrifying bacteria are not dominant bacteria in the sewage, most of the carbon sources are utilized by other microorganisms, so that resource waste and secondary pollution are caused.
In this regard, there is a problem in the related art that a carbon source having selectivity, such as polyhydroxyalkanoate, is selectively utilized by denitrifying bacteria, thereby improving the utilization efficiency of the carbon source by denitrifying bacteria, but the selectivity is not absolute, other bacteria which can utilize polyhydroxyalkanoate may still exist in sewage, and meanwhile, the utilization of polyhydroxyalkanoate by denitrifying bacteria is decomposed into small molecules first and then utilized, in this process, the small molecules can still be utilized by other microorganisms, and on the other hand, the energy utilization rate of such carbon source is lower than that of other polysaccharides, which results in the reduction of the denitrification efficiency.
Based on the above, the application provides a sewage treatment agent based on denitrifying bacteria and a preparation method thereof, which have good denitrification effect, and the specific embodiments of the application are described in detail below.
In a first aspect, the present invention provides a method for preparing a denitrifying bacteria-based sewage treatment agent, comprising the steps of:
s10: adding carbon source particles into a silane coupling agent KH550 aqueous solution, and coupling to obtain a silanized carbon source material, wherein the carbon source particles comprise at least one of alkali modified corncob particles and alkali modified wheat straw particles;
s20: adding silanized carbon source particles into denitrifying bacteria bacterial liquid, and uniformly mixing to obtain a first mixed liquid;
s30: adding polyvinyl alcohol, sodium alginate and cellulose into water, and uniformly mixing to obtain a second mixed solution;
s40: uniformly mixing the first mixed solution and the second mixed solution, then dripping the mixed solution into the first crosslinking solution, and curing and crosslinking to obtain gel microspheres;
s50: and adding the gel microspheres into the second crosslinking solution, and further crosslinking to obtain the sewage treatment agent.
According to the method, denitrifying bacteria are combined with carbon source particles, polyvinyl alcohol and sodium alginate are used for embedding the carbon source particles combined with the denitrifying bacteria and cellulase, the sewage treatment agent is obtained after two times of crosslinking, the carbon source particles in the sewage treatment agent can be directly utilized by the denitrifying bacteria, meanwhile, the cellulase can also promote the utilization of the denitrifying bacteria to the carbon source particles, and in addition, the polyvinyl alcohol and sodium alginate gel subjected to secondary crosslinking can slow down the outward permeation of decomposition products of the carbon source particles, so that most of carbon sources in the sewage treatment agent are utilized by the denitrifying bacteria, the denitrification reaction is promoted, the denitrification effect is improved, and the total nitrogen content in sewage is reduced.
According to the application, in step S10, the carbon source particles are subjected to silanization treatment, and the adhesion force on the surfaces of the carbon source particles can be effectively improved through silanization treatment, so that the loading capacity of denitrifying bacteria is improved, more denitrifying bacteria are directly contacted with the carbon source particles, and the carbon source particles are better utilized for denitrification reaction; in addition, the carbon source particles can comprise alkali modified corncob particles and alkali modified wheat straw particles, the corncob particles and the wheat straw particles are common agricultural and sideline products, the cost is low, the carbon source particles belong to high-quality carbon sources, the content of anti-biodegradation substances such as lignin can be effectively reduced by carrying out alkali treatment on the carbon source particles, and meanwhile, the specific surface area of the particles can be effectively increased, so that the loading capacity of the carbon source particles to denitrifying bacteria is increased.
In step S20, the silanized carbon source particles are added into the denitrifying bacteria bacterial liquid and mixed uniformly, so as to make denitrifying bacteria adsorbed on the surfaces of the silanized carbon source particles as much as possible, thereby improving the utilization efficiency of the denitrifying bacteria on the carbon source.
In the step S30, polyvinyl alcohol and sodium alginate are common microorganism coating materials, the biocompatibility is good, and the second mixed solution also comprises cellulase, so that in the sewage treatment process, the cellulase can promote the decomposition of carbon source particles, so that the carbon source particles are easier to be utilized by denitrifying bacteria, the denitrification efficiency can be improved, meanwhile, in the subsequent steps, polyethylene glycol and sodium alginate are used for embedding the carbon source particles combined with denitrifying bacteria and the cellulase, the cellulase and denitrifying bacteria can be effectively immobilized, and meanwhile, due to the silanization treatment of the carbon source particles, the polyvinyl alcohol and the sodium alginate can well coat the carbon source particles, and although the immobilization coating can effectively protect the denitrifying bacteria and prevent the denitrifying bacteria from losing, the activity of the denitrifying bacteria can be influenced, so that the denitrifying bacteria can decompose the carbon source particles, and with the utilization of the denitrifying bacteria to the carbon source particles, the space inside the sewage treatment agent is increased, the denitrifying bacteria can grow and propagate in the gel particles, and the denitrification effect is improved.
In step S40, the first mixed solution and the second mixed solution are uniformly mixed and then are dripped into the first crosslinking solution to obtain gel microspheres, the gel microspheres can well fix carbon source particles combined with denitrifying bacteria and cellulase, have good protection effects on the denitrifying bacteria and the cellulase, and meanwhile, the specific surface area of the sewage treatment agent can be effectively increased by preparing the gel microspheres, so that the mass transfer effect between the inside of the sewage treatment agent and sewage is improved, and the diffusion of nitrate radical into the inside of the sewage treatment agent and the escape of nitrogen are promoted. On the other hand, the first mixed solution and the second mixed solution are directly mixed, and since the first mixed solution also contains excessive denitrifying bacteria which are not combined with silanized carbon source particles, the free denitrifying bacteria can be immobilized by direct mixing, and it is understood that although the immobilized denitrifying bacteria are not in direct contact with the carbon source particles, the decomposition products of the internal carbon source particles can be utilized, so that the utilization rate of the denitrifying bacteria to the carbon source particles can be further improved, and the outward penetration of the decomposition products of the carbon source particles can be slowed down.
In step S50, the gel microsphere is subjected to secondary crosslinking in the second crosslinking solution, and the purpose of the secondary crosslinking is to further improve the crosslinking density of the surface layer of the gel microsphere, so that the strength of the sewage treatment agent can be improved, and meanwhile, the outward permeation of the decomposition products of the carbon source particles is slowed down while the mass transfer effects of small molecules such as nitrate, nitrogen and metabolic products of denitrifying bacteria are not influenced, so that the utilization efficiency of the denitrifying bacteria on the carbon source is further improved.
Based on this, in the sewage treatment agent obtained by the method, denitrifying bacteria are firstly loaded on carbon source particles and then coated, besides the advantages of immobilized bacteria, the utilization efficiency of the denitrifying bacteria on the carbon source particles can be improved, so that the denitrification reaction is promoted, and it is understood that compared with the method that the carbon source particles and the denitrifying bacteria are directly embedded at the same time, the denitrifying bacteria have poorer utilization effect on the carbon source particles due to immobilization, the denitrifying bacteria utilize the carbon source particles to rely on mass transfer effect, the utilization of the carbon source particles is unfavorable, if the crosslinking density is overlarge, the mass transfer effect is poor, the utilization efficiency of the carbon source particles is low, the denitrification efficiency is also reduced, and if the crosslinking density is too small, the decomposed matters of the carbon source particles are easy to permeate outwards, so that the carbon source is lost, and the utilization rate of the denitrifying bacteria on the carbon source particles is also reduced, so that the problems can be solved after the denitrifying bacteria are loaded and embedded; on the other hand, the immobilized microbial inoculum has the problems that although the immobilized denitrifying bacteria can prevent the denitrifying bacteria from losing, the activity of the denitrifying bacteria is affected by immobilization, and the denitrifying bacteria are loaded by a carbon source material, so that the carbon source material provides space for the growth and propagation of the denitrifying bacteria while being consumed, thereby improving the activity and the denitrification effect; in addition, through secondary crosslinking, the outward permeation of decomposition products of the carbon source material can be effectively avoided, and the utilization efficiency of denitrifying bacteria on the carbon source is further improved, so that the sewage treatment agent has a good denitrification effect.
As one example, the carbon source particles are alkali modified corncob particles, obtained by the following method: crushing the corncob raw material, sieving with a 100-mesh sieve, soaking in a 2% sodium hydroxide aqueous solution for 24 hours, removing and drying to obtain alkali modified corncob particles.
In some embodiments, in step S10, the dosage ratio of carbon source particles to aqueous solution of silane coupling agent KH550 is 1g: 10-50 mL, and the mass percentage of the aqueous solution of the silane coupling agent KH550 is 1-5%.
In some embodiments, the ratio of the carbon source particles to the aqueous solution of the silane coupling agent KH550 and the mass percent of the aqueous solution of the silane coupling agent KH550 are specifically defined, and under the condition, the carbon source particles can be fully silanized, so that the adsorption effect of the carbon source particles on denitrifying bacteria is further improved, the utilization rate of the carbon source particles by the denitrifying bacteria is improved, and the denitrification effect of the sewage treatment agent is further improved.
In some embodiments, in step S10, the mixing condition is stirring for 4-12 hours at 30-60 ℃.
In some embodiments, in step S20, the amount ratio of silanized carbon source particles to denitrifying bacteria liquid is 1g: 5-50 mL, and the OD600 of the denitrifying bacteria bacterial liquid is 0.8-1.2.
In some embodiments, the ratio of the usage amount of the silanized carbon source particles to the denitrifying bacteria bacterial liquid and the OD600 of the denitrifying bacteria bacterial liquid are specifically limited, and under the condition, the carbon source particles can fully load the denitrifying bacteria, so that the number of the denitrifying bacteria directly combined on the surfaces of the carbon source particles is further increased, the utilization rate of the carbon source particles by the denitrifying bacteria is further increased, the activity of the denitrifying bacteria in the sewage treatment agent is also increased, and the denitrification effect of the sewage treatment agent is further improved. The OD600 of the bacterial fluid is an optical density measurement used to measure the concentration or cell density of a microbial culture. OD (optical density) refers to the degree of absorption of light as it passes through a liquid sample. OD600 is an optical density value measured under light with a wavelength of 600 nm and can represent the concentration of microorganisms in the bacterial liquid.
In some embodiments, denitrifying bacteria may include Pseudomonas spPseudomonas sp) Pseudomonas putida @Pseudomonas putida) Bacillus subtilis @Bacillus subtilis) At least one of them. It is to be understood that denitrifying bacteria are not limited to the above, but denitrifying bacteria known in the art may be selected as needed. As an example, the present application uses Pseudomonas from China center for type culture Collection of microorganismsPseudomonas sp) The strain is CICC 25068, and is subjected to rejuvenation and expansion culture for later use.
In some embodiments, in step S20, the mixing condition is stirring for 2-6 hours at 20-35 ℃.
In some embodiments, in step S30, the dosage ratio of polyvinyl alcohol, sodium alginate, and water is 10g: 1-5 g: 20-100 mL, and the concentration of the cellulase in the second mixed solution is 10-200U/mL.
In some embodiments, the dosage ratio of the polyvinyl alcohol, the sodium alginate and the water and the concentration of the cellulase in the second mixed solution are specifically limited, under the condition, gel with proper crosslinking density can be obtained, denitrifying bacteria and the cellulase are better immobilized, meanwhile, loss of decomposition products of carbon source particles can be effectively reduced after secondary crosslinking, and the denitrification reaction is promoted; the cellulase can decompose cellulose in the carbon source particles more effectively, promote the utilization of the carbon source particles by denitrifying bacteria, promote the denitrification reaction and improve the denitrification effect. Further preferably, the dosage ratio of polyvinyl alcohol, sodium alginate and water is 10g: 1-5 g: 20-50 mL, the crosslinking degree is better at this time, and the utilization rate of denitrifying bacteria to carbon source particles can be further improved.
As one example, the cellulase is an acid cellulase. Because the preparation of the sewage treatment agent and the sewage treatment process, the acid cellulase has better activity.
It can be understood that the cellulase in the second mixed solution is added finally, polyvinyl alcohol and sodium alginate are heated and dissolved, and the cellulase is added after cooling, and the second mixed solution is obtained after uniform mixing.
In some embodiments, in step S40, the ratio of the amount of the first mixed solution to the amount of the second mixed solution is 1: 5-10. At the moment, the two are mixed and then crosslinked to obtain gel with good strength, and carbon source particles and cellulase can be effectively immobilized.
In some embodiments, in step S40, the first crosslinking solution is a saturated boric acid solution comprising 2-5 wt% calcium chloride. The polyvinyl alcohol and sodium alginate aqueous solution are crosslinked under the action of calcium ions and boric acid, and free denitrifying bacteria, cellulase and carbon source particles combined with the denitrifying bacteria are coated to obtain gel microspheres.
In some embodiments, in step S40, the curing and crosslinking time is 20 to 30 hours.
In some embodiments, in step S40, the gel microspheres are obtained by filtration and washing after curing and crosslinking.
In some embodiments, in step S50, the second crosslinking solution is a saturated boric acid solution comprising 0.5-2 wt% glutaraldehyde, 2-5 wt% calcium chloride. When boric acid is used for crosslinking polyvinyl alcohol, borate reacts with the polyvinyl alcohol to negatively charge the polymer chain belt, and further crosslinking of the polyvinyl alcohol is affected under the action of static electricity, so that the crosslinking density is relatively reduced, glutaraldehyde is used for further crosslinking, the influence of the static electricity is overcome, the polyvinyl alcohol chain is further crosslinked, the crosslinking density of the surface of the gel microsphere is further improved, and the outflow of carbon sources and denitrifying bacteria can be further reduced.
In some embodiments, the pH of the second crosslinking solution is 2 to 5.
In some embodiments, in step S50, the further crosslinking is performed for a period of 1 to 6 hours.
In a second aspect, the present application provides a denitrifying bacteria-based sewage treatment agent, prepared according to the method of any one of the embodiments of the first aspect.
According to the application, the sewage treatment agent is prepared by the method according to any embodiment of the first aspect, so that the sewage treatment agent has the beneficial effects of the first aspect.
In a third aspect, the present application provides a method for wastewater treatment comprising: adding the sewage treatment agent prepared by the method according to any one of the first aspect or the sewage treatment agent according to any one of the second aspect to sewage, and performing denitrification treatment to obtain treated sewage.
In some embodiments, the amount of the sewage treatment agent added is 50-250 g/L.
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are on a mass basis, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
Preparation of sewage treatment agent:
100g of alkali modified corncob particles are soaked in 3wt% of aqueous solution of a silane coupling agent KH550, stirred and reacted for 6 hours at 45 ℃, filtered and washed, and dried at 60 ℃ to obtain silanized corncob particles;
10g of silanized corncob particles are added into 100mL of pseudomonas liquid (CICC 25068) with the OD600 of 1, and stirred for 4 hours at the temperature of 30 ℃ to obtain a first mixed liquid;
180g of polyvinyl alcohol and 30g of sodium alginate are heated and dissolved in 900mL of water, 9g of acid cellulase with the enzyme activity of 10000U/g is added after cooling, and a second mixed solution is obtained;
uniformly mixing the first mixed solution and the second mixed solution, dripping the mixture into a saturated boric acid solution of 3wt% of calcium chloride, solidifying and crosslinking for 24 hours, filtering and washing, and drying at 40 ℃ to obtain gel microspheres;
and adding the gel microspheres obtained above into a saturated boric acid solution containing 1wt% of glutaraldehyde and 3wt% of calcium chloride, further crosslinking for 2 hours, filtering and washing, and drying at 40 ℃ to obtain the sewage treatment agent.
Example 2
Preparation of sewage treatment agent:
100g of alkali modified corncob particles are soaked in 3wt% of aqueous solution of a silane coupling agent KH550, stirred and reacted for 6 hours at 45 ℃, filtered and washed, and dried at 60 ℃ to obtain silanized corncob particles;
10g of silanized corncob particles are added into 100mL of pseudomonas liquid (CICC 25068) with the OD600 of 1, and stirred for 4 hours at the temperature of 30 ℃ to obtain a first mixed liquid;
heating and dissolving 150g of polyvinyl alcohol and 25g of sodium alginate in 900mL of water, cooling, and adding 9g of acidic cellulase with the enzyme activity of 10000U/g to obtain a second mixed solution;
uniformly mixing the first mixed solution and the second mixed solution, dripping the mixture into a saturated boric acid solution of 3wt% of calcium chloride, solidifying and crosslinking for 24 hours, filtering and washing, and drying at 40 ℃ to obtain gel microspheres;
and adding the gel microspheres obtained above into a saturated boric acid solution containing 1wt% of glutaraldehyde and 3wt% of calcium chloride, further crosslinking for 2 hours, filtering and washing, and drying at 40 ℃ to obtain the sewage treatment agent.
Comparative example 1
Preparation of sewage treatment agent:
10g of alkali modified corncob particles are added into 100mL of pseudomonas liquid (CICC 25068) with the OD600 of 1, and stirred for 4 hours at the temperature of 30 ℃ to obtain a first mixed liquid;
180g of polyvinyl alcohol and 30g of sodium alginate are heated and dissolved in 900mL of water, 9g of acid cellulase with the enzyme activity of 10000U/g is added after cooling, and a second mixed solution is obtained;
uniformly mixing the first mixed solution and the second mixed solution, dripping the mixture into a saturated boric acid solution of 3wt% of calcium chloride, solidifying and crosslinking for 24 hours, filtering and washing, and drying at 40 ℃ to obtain gel microspheres;
and adding the gel microspheres obtained above into a saturated boric acid solution containing 1wt% of glutaraldehyde and 3wt% of calcium chloride, further crosslinking for 2 hours, filtering and washing, and drying at 40 ℃ to obtain the sewage treatment agent.
Comparative example 2
Preparation of sewage treatment agent:
100g of alkali modified corncob particles are soaked in 3wt% of aqueous solution of a silane coupling agent KH550, stirred and reacted for 6 hours at 45 ℃, filtered and washed, and dried at 60 ℃ to obtain silanized corncob particles;
10g of silanized corncob particles are added into 100mL of pseudomonas liquid (CICC 25068) with the OD600 of 1, and stirred for 4 hours at the temperature of 30 ℃ to obtain a first mixed liquid;
180g of polyvinyl alcohol and 30g of sodium alginate are heated and dissolved in 900mL of water to obtain a second mixed solution;
uniformly mixing the first mixed solution and the second mixed solution, dripping the mixture into a saturated boric acid solution of 3wt% of calcium chloride, solidifying and crosslinking for 24 hours, filtering and washing, and drying at 40 ℃ to obtain gel microspheres;
and adding the gel microspheres obtained above into a saturated boric acid solution containing 1wt% of glutaraldehyde and 3wt% of calcium chloride, further crosslinking for 2 hours, filtering and washing, and drying at 40 ℃ to obtain the sewage treatment agent.
Comparative example 3
Preparation of sewage treatment agent:
100g of alkali modified corncob particles are soaked in 3wt% of aqueous solution of a silane coupling agent KH550, stirred and reacted for 6 hours at 45 ℃, filtered and washed, and dried at 60 ℃ to obtain silanized corncob particles;
10g of silanized corncob particles are added into 100mL of pseudomonas liquid (CICC 25068) with the OD600 of 1, and stirred for 4 hours at the temperature of 30 ℃ to obtain a first mixed liquid;
180g of polyvinyl alcohol and 30g of sodium alginate are heated and dissolved in 900mL of water, 9g of acid cellulase with the enzyme activity of 10000U/g is added after cooling, and a second mixed solution is obtained;
and uniformly mixing the first mixed solution and the second mixed solution, dripping the mixture into a saturated boric acid solution of 3wt% of calcium chloride, solidifying and crosslinking for 24 hours, filtering and washing, and drying at 40 ℃ to obtain gel microspheres which are used as a sewage treatment agent.
And (3) detecting denitrification effect:
respectively adding 30g of the sewage treatment agents obtained in the examples and the comparative examples into 200mL of synthetic wastewater, continuously culturing for 5d under the condition of oxygen isolation, sampling the water inlet and outlet of the reactor at fixed time every day, standing the reactor for 30 min before sampling, collecting a certain amount of liquid sample, filtering with a 0.45 μm filter membrane, and testing NO 3 - The N index and the test standard are HJ/T346-2007 ultraviolet spectrophotometry for measuring nitrate nitrogen in water quality. And simultaneously, replacing all water bodies in the reactor with new 200mL of artificial synthetic wastewater. Calculation of NO 3 - The removal rate of N and the results are shown in Table 1.
Preparing artificial synthetic wastewater: placing tap water for two days, boiling to remove dissolved oxygen in water, and adding KNO to ensure good proliferation of denitrifying bacteria 3 And KH 2 PO 4 So that N: P is 5:1, KNO thereof 3 The concentration was 25mg/L.
TABLE 1
As is clear from Table 1, NO in the wastewater treatment agent obtained in each example 3 - The removal rate of N is superior to that of each comparative example, which shows that the sewage treatment agent provided by the application has good denitrification effect. The reason why the denitrification effect of the sewage treatment agent obtained in comparative example 1 is the worst is probably that the carbon source particles are not subjected to silanization treatment, so that the loading amount of denitrifying bacteria on the carbon source particles is low, and a large amount of denitrifying bacteria are dissociated in the first mixed solution, thereby directly solidifyingThe denitrifying bacteria are fixed in the gel, so that the efficiency of utilizing carbon source particles by the denitrifying bacteria is lower, and the activity of the immobilized denitrifying bacteria is lower, so that the denitrifying effect is poorer; the reason why the denitrification effect of comparative example 2 is inferior to that of the example in the early stage of sewage treatment is probably because the denitrifying bacteria need to decompose the carbon source particles into small molecules before further use, so that the process adapting to the carbon source is provided, and the cellulase can promote the decomposition of the carbon source particles and reduce the time adapting to the carbon source, thereby improving the denitrification effect of the sewage treatment agent in the early stage; the comparative example 3 is slightly different from the example in the early stage of effluent treatment and is somewhat different from the example in the later stage, probably because the cross-linking density of the outer layer of the sewage treatment agent is small, so that the decomposition products of carbon source particles are more likely to permeate into the water body due to the concentration difference, and the denitrification effect in the later stage is reduced. In addition, since the test was performed in an ideal artificial wastewater, there was not much microorganism competing with it for the carbon source in the system, and it was understood that the sewage treatment effect of comparative example 3 may be worse in practical use. The embodiment has good denitrification effect, which shows that although the method can further improve the crosslinking density of the outer layer and slow down the exudation speed of the decomposition products of the carbon source particles, the method can not influence the transmission of small molecules, and the method can provide growth and propagation space for denitrifying bacteria through the built-in high-quality carbon source of the sewage treatment agent, thereby effectively promoting the denitrification reaction, having good denitrification effect, and being expected to be applied to the denitrification stage of sewage treatment to reduce the total nitrogen content in sewage.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (4)
1. A method for preparing a denitrifying bacteria-based sewage treatment agent, comprising the steps of:
s10: adding carbon source particles into a silane coupling agent KH550 aqueous solution, and coupling to obtain silanized carbon source particles, wherein the carbon source particles comprise at least one of alkali modified corncob particles and alkali modified wheat straw particles, and the dosage ratio of the carbon source particles to the silane coupling agent KH550 aqueous solution is 1g: 10-50 mL, wherein the mass percentage of the aqueous solution of the silane coupling agent KH550 is 1-5%;
s20: adding the silanized carbon source particles into denitrifying bacteria bacterial liquid, and uniformly mixing to obtain a first mixed liquid;
s30: adding polyvinyl alcohol, sodium alginate and cellulose into water, and uniformly mixing to obtain a second mixed solution; wherein the dosage ratio of the polyvinyl alcohol to the sodium alginate to the water is 10g: 1-5 g: 20-100 mL, wherein the concentration of the cellulase in the second mixed solution is 10-200U/mL;
s40: after uniformly mixing the first mixed solution and the second mixed solution, dropwise adding the first mixed solution into the first crosslinking solution, and curing and crosslinking to obtain gel microspheres, wherein the dosage ratio of the first mixed solution to the second mixed solution is 1: 5-10, wherein the first crosslinking solution is a saturated boric acid solution containing 2-5wt% of calcium chloride;
s50: and adding the gel microspheres into a second crosslinking solution, and further crosslinking to obtain the sewage treatment agent, wherein the second crosslinking solution is a saturated boric acid solution comprising 0.5-2wt% of glutaraldehyde and 2-5wt% of calcium chloride.
2. The method according to claim 1, wherein in the step S20, the ratio of the amount of the silanized carbon source particles to the denitrifying bacteria liquid is 1g: 5-50 mL, OD of the denitrifying bacteria liquid 600 0.8 to 1.2.
3. A denitrifying bacteria-based sewage treatment agent, characterized by being prepared according to the method of claim 1 or 2.
4. A method for wastewater treatment comprising: adding the sewage treatment agent prepared by the method according to claim 1 or 2 or the sewage treatment agent according to claim 3 into sewage, and performing denitrification treatment to obtain treated sewage.
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JPH01168349A (en) * | 1987-11-12 | 1989-07-03 | Aichi Pref Gov | Method for fixing biocatalyst |
CN111500567A (en) * | 2020-04-28 | 2020-08-07 | 深圳文科园林股份有限公司 | Preparation method of co-immobilized pellet for synchronous nitrification and denitrification and co-immobilized pellet |
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JPH01168349A (en) * | 1987-11-12 | 1989-07-03 | Aichi Pref Gov | Method for fixing biocatalyst |
CN111500567A (en) * | 2020-04-28 | 2020-08-07 | 深圳文科园林股份有限公司 | Preparation method of co-immobilized pellet for synchronous nitrification and denitrification and co-immobilized pellet |
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