CN113149350A - Chelated biological catalytic particles for in-situ restoration of water body and preparation method thereof - Google Patents

Abstract

The invention relates to a chelating biocatalysis particle for water body in-situ restoration and a preparation method thereof. By utilizing the water in-situ remediation chelated biological catalytic particles, nitrogen, phosphorus and algae in the eutrophic water body/black and odorous water body can be efficiently removed, the growth of the algae is inhibited, and the water quality of the inferior V-type water body can be restored to be superior to that of the III-type water body within 2 months. The water in-situ restoration chelated biological catalysis particles have the advantages of easily available raw materials, simple preparation method, easy realization of industrial production of products, high water restoration rate, low restoration cost and wide popularization and application prospects.

Description

Chelated biological catalytic particles for in-situ restoration of water body and preparation method thereof

Technical Field

The invention relates to a chelating biocatalysis particle for water body in-situ remediation and a preparation method thereof, belonging to the technical field of water pollution control.

Background

Blue sky blue water is the most ideal natural ecological environment for modern people. And as part of untreated or substandard sewage and agricultural non-point source pollutants are discharged into surface water, the water supply function of the water body as a water source is influenced, and aquatic organisms are damaged. The main pollutants causing surface water pollution are nitrogen and phosphorus, which are expressed as water eutrophication and are easy to generate water bloom and even cause black and smelly water and bottom mud. Therefore, the main task of water body restoration is to reduce the nitrogen and phosphorus concentration of the water body and control the growth of algae. At present, the water body restoration is mainly based on an in-situ restoration technology and mainly comprises the steps of adding a medicament and cultivating aquatic plants. The addition of the medicament has the defects of high investment and difficult long-term maintenance of the repairing effect. The aquatic vegetation cultivation mainly comprises an artificial wetland technology and an artificial floating island technology, the restoration effect is obviously limited by regions and seasons, and the restoration speed is slow.

Therefore, the research and the invention of a new technology or a new material which can quickly and effectively reduce the nitrogen and phosphorus concentration of the water body for a long time and control the growth of algae have important significance for solving the problems of water body eutrophication and black and odorous.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a water body in-situ remediation chelated biological catalytic particle and a preparation method thereof, and the specific technical scheme is as follows:

the chelating biocatalysis particle for in-situ water body restoration comprises the following components in percentage by volume:

the sum of the volume percentages of the components is 100 percent.

As an improvement of the technical scheme, the bioactive agent is one or more of fulvic acid, ethylene diamine tetraacetic acid and biogel.

As an improvement of the technical scheme, the bioactive agent is prepared by mixing fulvic acid, ethylene diamine tetraacetic acid and biogel according to the volume ratio of (20-30) to (40-60).

As an improvement of the technical scheme, the catalyst is one or more of zero-valent copper powder, zero-valent nickel powder and zero-valent vanadium.

As an improvement of the technical scheme, the catalyst is prepared by mixing zero-valent copper powder, zero-valent nickel powder and zero-valent vanadium according to the volume ratio of (55-70) to (25-35) to (5-10).

As an improvement of the technical scheme, the adhesive is prepared by mixing polyvinyl alcohol and phenolic resin according to the volume ratio of (40-60) to (40-60).

The preparation method of the water body in-situ remediation chelated biocatalytic particle comprises the following steps:

step one, preparing a bioactive agent, a catalyst and an adhesive;

step two, mixing the single-substance iron powder and the activated carbon powder to form a mixture A;

adding a catalyst into the mixture A, fully mixing to form a mixture B, and staying for 2 hours;

adding the bioactive agent into the mixture B, and fully mixing to form a mixture C;

step five, mixing the adhesive into the mixture C, and fully stirring to form a mixture D;

step six, adding water into the mixture D to prepare 20-40 mm particles;

and seventhly, naturally drying the prepared particles for 1-2 days at normal temperature to obtain the water in-situ restoration chelated biological catalytic particles.

The bioactive agent is natural biogel. The product is rich in trace nutrient elements beneficial to the growth of microorganisms, and has the effects of promoting the growth of microorganisms and improving the activity of microorganisms.

Experiments were performed on the bioactive agents mentioned in the present invention:

the same aerobic activated sludge (the sludge concentration is 4100-. In the experiment, the control group is not added with the bioactive agent; the bioactive agents are added into the experimental groups, and the adding amount is 10 mg/L. Experiments show that in the nitrification reaction test of the aerobic activated sludge, NH is taken as inlet water₄ ⁺When the-N concentration is 100mg/L and the hydraulic retention time is 2 hours, the adding of the bioactive agent can be used for adding NH₄ ⁺The removal load of N is increased from 25.8mg/L/h) to 32.2 mg/(L.h), which is increased by 24.8 percent; in the nitrification reaction test of the anaerobic activated sludge, NO is added when water is fed₃ ^-When the-N concentration is 100mg/L and the hydraulic retention time is 4h, the addition of the bioactive agent can be used for adding NO₃ ^-The removal load of-N is increased from 15.8mg/L/h to 22.9mg/L/h, which is increased by 44.9%. The result shows that the addition of the biological active agent can effectively improve the biological activity of nitrobacteria and denitrifying bacteria and strengthen the biological denitrification reaction process.

The invention has the beneficial effects that:

the water body in-situ remediation chelated biological catalytic particles utilize the self iron-carbon (Fe-C) micro-electrolysis reaction of the particles in water to continuously release ferrous ions (Fe)²⁺) Trivalent iron ion (Fe)³⁺) And reducing hydrogen ([ H ]]/H₂). Wherein the added bioactive agent can be mixed with Fe²⁺/Fe³⁺The complex can adjust the release speed of iron ions, is suitable for being biologically utilized, promotes the growth of microorganisms, adjusts the ecological structure of water microorganisms, ensures the diversity of microorganism biomass and microorganism population and accelerates the water body restoration speed.

The micro-electrolysis reaction of the water in-situ remediation chelated biological catalytic particles can strengthen the oxidation of ammonia nitrogen, and meanwhile, the microorganisms attached to the surfaces of the particles can utilize Fe²⁺And [ H]/H₂As electron donorsAutotrophic denitrification is adopted, and the control of the nitrogen concentration of the water body is realized under the condition of no additional carbon source.

Fe generated in water body in-situ remediation and chelating biocatalytic particle reaction process³⁺Has strong precipitation effect on phosphorus to generate FePO₄·2H₂And the total phosphorus concentration in the water body can be effectively controlled by the precipitation of O and the like, and no additional medicament is required to be added.

The water body in-situ remediation chelates the micro-electrolysis reaction of the biological catalytic particles in water, and the micro-current is continuously released, so that the cell structure of algae can be effectively destroyed, the algae concentration in the water body is reduced, and the algae growth is inhibited.

The water in-situ remediation chelated biological catalysis particles can realize effective control of nitrogen, phosphorus and algae in the water, no additional medicament is needed, the cost is low, no secondary pollution is caused, a simple remediation method for eutrophic water and black and odorous water can be provided by the application of the particles, and meanwhile, the remediation cost is reduced.

The water in-situ remediation chelated biocatalytic particle has the advantages of simple and easily-obtained raw materials, simple preparation method, no need of high-temperature sintering in the preparation process, low production cost and easy realization of industrial production of products.

Drawings

FIG. 1 is a diagram showing the effect of suspending and throwing water into an artificial floating island to restore chelated biocatalytic particles in situ.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example 1

The water in-situ restoration chelated biocatalytic particles are prepared from simple substance iron powder, activated carbon powder, a bioactive agent consisting of fulvic acid, ethylene diamine tetraacetic acid and biogel, a catalyst consisting of zero-valent copper powder, zero-valent nickel powder and zero-valent vanadium powder, and an adhesive consisting of polyvinyl alcohol and phenolic resin.

The preparation method of the chelating biocatalytic particle for in-situ water body remediation specifically comprises the following steps:

step one, preparing a biological active agent (fulvic acid, ethylene diamine tetraacetic acid and biogel), a catalyst (zero-valent copper powder, zero-valent nickel powder and zero-valent vanadium powder) and an adhesive (polyvinyl alcohol and phenolic resin) according to a volume ratio.

Step two, mixing the simple substance iron powder and the activated carbon powder according to the volume ratio according to the raw material composition to form a mixture A.

And step three, adding the catalyst into the mixture A according to the volume ratio, fully mixing to form a mixture B, and staying for 2 hours.

And step four, adding the bioactive agent into the mixture B according to the volume ratio, and fully mixing to form a mixture C.

And step five, mixing the adhesive into the mixture C according to the volume ratio, and fully stirring to form a mixture D.

And step six, adding water into the mixture D according to the volume ratio to prepare 20-40 mm particles.

And seventhly, naturally drying the prepared particles for 1-2 days at normal temperature to obtain the water in-situ restoration chelated biological catalytic particles.

In the above manner, catalytic particles used in example 2 (containing formulations 1-1, 1-2, 1-3), comparative example 1 (containing formulations 1-1, 2-2, 2-3), comparative example 2 (containing formulations 1-1, 3-2, 3-3) and comparative example 3 (containing formulations 1-1, 4-2, 4-3) were prepared.

Example 2

TABLE 1

Table 1 shows 3 formulations of the chelating biocatalytic particles for in situ remediation of water according to the present invention. In this example, the effect of the added amount of the bioactive agent and the catalyst in the chelated biocatalytic particles for in situ water body remediation on the water body remediation effect is compared (table 1). In the embodiment, each group of laboratory tests adopts water body in-situ remediation chelated biological catalytic particles to carry out water body remediation on 2L (in the test, the inner diameter of a reactor is 15cm, and the height of the reactor is 15cm) of eutrophic surface water. The adding amount of the chelated biological catalytic particles for water body in-situ remediation is controlled to be 4 mL. The used eutrophic surface water is taken from an actual eutrophic water body, and the concentrations of ammonia nitrogen, total phosphorus and chlorophyll a are respectively 2.6mg/L, 2.8mg/L, 0.28mg/L and 290mg/L before restoration, and the eutrophic surface water is a poor V-type water body (GB 3838-2002). This example examined the remediation effect within 30 days of the in situ remediation of chelated biocatalytic particles by dosing with a water body.

The water remediation test was performed at room temperature (20-25 ℃) and a shaker was used to provide a vibration frequency of 30rpm to simulate natural water disturbance. When the repair is continuously carried out for 30 days, in the formula 1-1 group, the average removal rates of ammonia nitrogen, total phosphorus and chlorophyll a are 72.0%, 62.6%, 79.2% and 66.0% respectively; in the formula 1-2 groups, the average removal rates of ammonia nitrogen, total phosphorus and chlorophyll a are respectively 61.8%, 50.6%, 78.1% and 66%; in the formulas 1-3, the average removal rates of ammonia nitrogen, total phosphorus and chlorophyll a are 73.3%, 55.7%, 68.4% and 52.4% respectively.

It is shown that the reduction of the dosage of the bioactive agent in the formula 1-2 (from 8% to 6%) reduces the biological activity of the nitrifying bacteria and the denitrifying bacteria in the water, resulting in a significant reduction of the removal rate of ammonia nitrogen and total nitrogen. Meanwhile, the reduction of the catalytic addition in the formulas 1 to 3 leads to the obvious reduction of the concentration of the total phosphorus and chlorophyll a, which shows that the reduction of the catalyst reduces the efficiency of catalytic internal electrolysis reaction, and leads to the reduction of the precipitation efficiency of iron ions to phosphate and the crushing capacity of internal electrolysis to algae.

Example 3 (application)

The formulation of the catalytic particles used in this example was the formulation 1-1 of example 2 (Table 1), and the preparation was also as described above.

The embodiment is applied to restoring eutrophic landscape water bodies in a Beijing park, and water body restoration is carried out by adopting a mode of artificial floating islands to three-dimensionally put in water body in-situ restoration chelated biological catalytic particles, as shown in figure 1. In this example, the amount of chelating biocatalytic particles added for in situ remediation of water is about 1 cubic meter of particles per 500 cubic meters of water (1 m)³/500m³)。

The landscape water body is seriously eutrophicated, and the concentrations of ammonia nitrogen, total phosphorus and chlorophyll a of the landscape water body before restoration are respectively 1.6-2.8 mg/L, 2.0-3.1 mg/L, 0.17-0.33 mg/L and 257.3-309 mg/L, so that the landscape water body is a poor V-class water body (GB 3838 + 2002).

This example examined the restoration effect within 60 days after the in situ restoration of chelated biocatalytic particles in a water body, as follows:

when the landscape water body is continuously restored for 30 days, the concentrations of ammonia nitrogen, total phosphorus and chlorophyll a in the landscape water body are respectively 0.33-0.89 mg/L, 0.59-1.1 mg/L, 0.05-0.16 mg/L and 90.1-93.5 mg/L, the average removal rates respectively reach 75.3%, 68.6%, 70.4% and 63.7%, and the landscape water body is superior to the IV water body (surface water environmental quality standard GB 3838 and 2002).

When the landscape water body is continuously restored for 2 months, the concentrations of ammonia nitrogen, total phosphorus and chlorophyll a in the landscape water body are respectively 0.12-0.18 mg/L, 0.22-0.29 mg/L, 0.03-0.08 mg/L and 40.6-56.0 mg/L, the removal rates respectively reach 91.3%, 87.9%, 76.0% and 84.1%, and the landscape water body is superior to a II-type water body (surface water environmental quality standard GB 3838-.

Comparative example 1

TABLE 2

Comparative example 1 compares the influence of the ratio of fulvic acid, ethylenediaminetetraacetic acid and biogel in the chelated biocatalytic particles for water in-situ remediation on the water remediation effect (table 2). In this comparative example, the test conditions and the test raw water were the same as those in example 1. This example examined the remediation effect within 30 days of the in situ remediation of chelated biocatalytic particles by dosing with a water body. When the repair is continuously carried out for 30 days, in the formula 1-1 group, the average removal rates of ammonia nitrogen, total phosphorus and chlorophyll a are 72.0%, 62.6%, 79.2% and 66.0% respectively; in the formula 2-2 group, the average removal rates of ammonia nitrogen, total phosphorus and chlorophyll a are respectively 64.6%, 57.5%, 84.5% and 71.2%; in the formulas 2-3, the average removal rates of ammonia nitrogen, total phosphorus and chlorophyll a are respectively 74.4%, 65.8%, 60.9% and 57.0%.

The formula 2-2 shows that the reduction of the addition amount of the biogel (from 50% to 40%) reduces the biological activity of nitrobacteria and denitrifying bacteria in water, so that the removal rate of ammonia nitrogen and total nitrogen is obviously reduced; the addition of the fulvic acid (20% is increased to 30%) enhances the removal capability of the complex precipitate of the total phosphorus by the catalytic particles, and shows that the addition of the fulvic acid is beneficial to the generation of electrolytic iron ions in the catalytic particles. In the formulas 2-3, the addition amount of the ethylenediaminetetraacetic acid is reduced (30% to 20%) and the removal rate of the total phosphorus and the algae is reduced, which shows that the complexing and precipitating effect of the ethylenediaminetetraacetic acid and iron ions plays a key role in removing the total phosphorus and the algae.

Comparative example 2

TABLE 3

Comparative example 2 compares the influence of the ratio of zero-valent copper, zero-valent nickel and zero-valent vanadium in the chelated biocatalytic particles for water body in-situ remediation on the water body remediation effect (table 3). In this comparative example, the test conditions and the test raw water were the same as those in example 1. This example examined the remediation effect within 30 days of the in situ remediation of chelated biocatalytic particles by dosing with a water body. When the repair is continuously carried out for 30 days, in the formula 1-1 group, the average removal rates of ammonia nitrogen, total phosphorus and chlorophyll a are 72.0%, 62.6%, 79.2% and 66.0% respectively; in the formula 3-2 group, the average removal rates of ammonia nitrogen, total phosphorus and chlorophyll a are 59.1%, 53.2%, 84.0% and 49.7% respectively; in the formula 3-3 groups, the average removal rates of ammonia nitrogen, total phosphorus and chlorophyll a are 71.1%, 49.2%, 54.3% and 70.2% respectively.

It is shown that in the formula 3-2, the reduction of the addition amount of the zero-valent vanadium (from 10% to 5%) reduces the electro-oxidation capability of the catalytic particles, resulting in a significant reduction in the removal rate of ammonia nitrogen and algae; and the increase of the addition amount of the zero-valent copper effectively accelerates the release of iron ions in the internal electrolysis process and improves the removal rate of the total lead. In the formulas 3-3, the reduction of the addition amount of the zero-valent nickel (30% to 20%) remarkably reduces the removal rate of the total phosphorus, which indicates that the addition of the zero-valent nickel is helpful for accelerating the generation of electrolytic iron ions in the catalytic particles. However, when the addition amount of the zero-valent nickel is reduced, the algae removal rate is obviously increased, which shows that the addition of the nickel can accelerate the internal electrolysis, but is not beneficial to the improvement of the electro-oxidation capability of the catalytic particles.

Comparative example 3

TABLE 4

Comparative example 3 compares the effect of the ratio of the binder polyvinyl alcohol to the phenolic resin in the chelated biocatalytic particle for in situ remediation of water on the porosity and strength of the particle (table 4). The formula 1-1, the formula 4-2 and the formula 4-3 are used for detecting the porosity, the particle strength and the water body restoration performance of the water body in-situ restoration chelated biological catalytic particles with different formulas by adopting the same preparation process flow. The results are as follows:

formulation 1-1: average porosity of 55.8% and average particle strength of 3.2kg/cm²The average removal rates of ammonia nitrogen, total phosphorus and chlorophyll a are 72.0%, 62.6%, 79.2% and 66.0% respectively; and (4) formula 4-2: average porosity of 64.0% and average particle strength of 2.2kg/cm²The average removal rates of ammonia nitrogen, total phosphorus and chlorophyll a are respectively 75.3%, 70.9%, 84.1% and 76.6%; and (4) formula 4-3: average porosity of 50.5% and average particle strength of 3.8kg/cm²The average removal rates of ammonia nitrogen, total phosphorus and chlorophyll a are 63.3%, 58.6%, 77.0% and 54.3% respectively.

The results show that the curing action of the phenolic resin ensures the strength of the particles, the strength of the particles is increased along with the increase of the adding amount of the phenolic resin, but the porosity of the particles is reduced, so that the processing capacity of the catalytic particles is influenced, and the removal rate of the pollutant concentration is reduced. It is noteworthy that an increase in the polyvinyl alcohol dosage results in a significant increase in the total nitrogen removal. The reason is that in the low-carbon-source water body remediation, the polyvinyl alcohol can be used as a good slow-release carbon source to promote the biological growth and the denitrification process.

The catalytic particles are used for long-term water body restoration after being thrown into a water body, and the requirement on the strength of the particles is low. The water body restoration process simultaneously comprises physicochemical restoration and biological restoration, and in the low-carbon-source water body restoration, the polyvinyl alcohol can be used as a good slow-release carbon source to promote biological growth and a denitrification process. Polyvinyl alcohol is therefore chosen instead of water glass. The purpose of the phenolic resin is to ensure the porosity of the particles while serving as a binder.

In the embodiment, the water in-situ remediation chelated biological catalytic particles realize the removal of nitrogen and phosphorus in the eutrophic water, and effectively control the propagation of algae. No additional medicament is needed, no secondary pollution is caused, a simple method for restoring eutrophic water bodies and black and odorous water bodies can be provided by applying the method, and the water body restoring cost is reduced. The water in-situ remediation chelated biological catalytic particles and the water remediation technology based on the water in-situ remediation chelated biological catalytic particles have wide popularization and application prospects.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (7)

1. The chelating biocatalysis particle for in-situ water body restoration is characterized by comprising the following components in percentage by volume:

the sum of the volume percentages of the components is 100 percent.

2. The chelated biocatalytic particle for in situ water body remediation of claim 1, wherein: the bioactive agent is one or more of fulvic acid, ethylene diamine tetraacetic acid and biogel.

3. The chelating biocatalytic particle for in situ water body remediation and the preparation method thereof as claimed in claim 2, wherein the chelating biocatalytic particle comprises: the biological active agent is prepared by mixing fulvic acid, ethylene diamine tetraacetic acid and biogel according to the volume ratio of (20-30) to (40-60).

4. The chelating biocatalytic particle for in situ water body remediation and the preparation method thereof as claimed in claim 1, wherein the chelating biocatalytic particle comprises: the catalyst is one or more of zero-valent copper powder, zero-valent nickel powder and zero-valent vanadium.

5. The chelating biocatalytic particle for in situ water body remediation of claim 4, wherein the chelating biocatalytic particle comprises: the catalyst is prepared by mixing zero-valent copper powder, zero-valent nickel powder and zero-valent vanadium according to the volume ratio of (55-65) to (20-35) to (5-10).

6. The chelating biocatalytic particle for in situ water body remediation and the preparation method thereof as claimed in claim 1, wherein the chelating biocatalytic particle comprises: the adhesive is prepared by mixing polyvinyl alcohol and phenolic resin according to the volume ratio of (40-60) to (40-60).

7. The method for preparing the chelated biocatalytic particles for in-situ water body remediation of claim 1, comprising the steps of:

step one, preparing a bioactive agent, a catalyst and an adhesive;

step two, mixing the single-substance iron powder and the activated carbon powder to form a mixture A;

adding a catalyst into the mixture A, fully mixing to form a mixture B, and staying for 2 hours;

adding the bioactive agent into the mixture B, and fully mixing to form a mixture C;

step five, mixing the adhesive into the mixture C, and fully stirring to form a mixture D;

step six, adding water into the mixture D to prepare 20-40 mm particles;

and seventhly, naturally drying the prepared particles for 1-2 days at normal temperature to obtain the water in-situ restoration chelated biological catalytic particles.

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