Black and odorous water composite treatment and restoration agent and preparation method thereof

Abstract

The application provides a black and odorous water composite treatment and repair agent and a preparation method thereof, and belongs to the technical field of sewage treatment. The treatment and repair agent integrates biological, chemical and physical treatment mechanisms. Graphene oxide modified basalt is used as a carrier to fix a composite microbial agent, and adsorbents and slow-release carbon sources are used as supplements. The adsorbents include biomass charcoal, oxidized biomass charcoal and activated biomass charcoal. The treatment and repair agent greatly overcomes the defects and restrictions of single treatment agents in treating complex black and odorous water, such as the complexity of needing to add different agents in stages and the single action of a single agent being unable to achieve comprehensive treatment effects. The application prepares the black and odorous water composite treatment and repair agent by the following method. The above-mentioned defects are overcome, the treatment process of black and odorous water is simplified, and multiple agents simultaneously play a role to achieve excellent treatment effects.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of sewage treatment, in particular to a novel high-efficiency black and odorous water composite treatment and repair agent and a preparation method thereof. BACKGROUND

[0002] Black and odorous water seriously damages the ecological environment, weakens the self-purification ability of water bodies, and endangers human health. Black and odorous water has complex causes and is difficult to treat, and therefore scientific treatment measures need to be taken according to local conditions. Current black and odorous water treatment technologies are classified into three types according to treatment mechanisms, namely, physical methods, chemical methods, and biological methods. Physical methods mainly include aeration, adsorption, and dredging of bottom mud. Chemical methods are based on flocculation oxidation and precipitation. Biological methods mainly use microorganisms, protozoa, plants, and biological agents to absorb, transform, and remove pollutants in water bodies to achieve the treatment goal. Physical methods can improve water quality, but their effects are limited, and they require high equipment and operation costs. Chemical methods can quickly remove most organic matter in water, but they cannot completely remove pollutants and have a large impact on the ecological environment. Biological methods have the advantages of ecological energy saving, low cost, high efficiency, and no secondary pollution, but they have some safety problems and limiting factors such as biological pollution, odor, environmental pollution, and mutation. In summary, single methods have certain limitations, and therefore although there are many studies on the treatment and repair of black and odorous water, many essential problems cannot be completely solved due to the limitations of treatment agents in actual treatment processes, and therefore the treatment agent for black and odorous water needs to be further researched. SUMMARY

[0003] The present application aims to provide a novel high-efficiency black and odorous water composite treatment and repair agent and a preparation method thereof to solve at least one technical problem in the background.

[0004] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0005] On the one hand, the present application provides a preparation method of a black and odorous water composite treatment and repair agent, which mainly comprises an appropriate biological agent, an adsorbent, and a slow-release carbon source, and the biological agent, the adsorbent, and the slow-release carbon source are loaded or fixed on an appropriate carrier by a certain technical means.

[0006] On the one hand, the present application provides a black and odorous water comprehensive treatment agent, which mainly comprises an appropriate biological agent, an adsorbent, and a slow-release carbon source, and the biological agent, the adsorbent, and the slow-release carbon source are fixed on an appropriate carrier by a certain technical means.

[0007] Preferably, the biological agent is a mixed bacterial agent mainly composed of Bacillus, photosynthetic bacteria, actinomycetes, nitrifying bacteria, and lactic acid bacteria.

[0008] Preferably, the adsorbent is biomass activated carbon or oxidized biomass activated carbon.

[0009] Preferably, the modified basalt fiber is modified by graphene oxide with different oxidation degrees.

[0010] Preferably, the preparation scheme of graphene oxide with different oxidation degrees is as follows:

[0011] Step one: 1.5 g of natural graphite powder and a certain amount of 98% concentrated sulfuric acid are added to a three-necked flask, the flask is placed in an ice water bath, and mechanical stirring is used for sufficient stirring reaction. Step two: a certain amount of potassium permanganate powder is slowly added to the three-necked flask under stirring, the reaction temperature is controlled at about 15°C, and when no purple gas is emitted, the stirring reaction is continued at room temperature for 2 h, and then left overnight. Step three: 100 ml of deionized water is added to the three-necked flask, the reaction temperature is controlled at about 95°C, and the stirring is continued for 30 min, then 30% H2O2 is added until no bubbles are generated in the reaction system, and then filtered while hot. Step four: the filter residue is washed with deionized water until the supernatant is neutral, and the filter residue is the GO paste.

[0012] Preferably, the concentration of concentrated sulfuric acid is 98%.

[0013] Preferably, the reaction temperature is 15°C.

[0014] Preferably, the concentration of hydrogen peroxide added is 20%.

[0015] Preferably, when preparing lightly oxidized graphene oxide, 200 ml of concentrated sulfuric acid and 5 g of potassium permanganate are added.

[0016] Preferably, when preparing heavily oxidized graphene oxide, 100 ml of concentrated sulfuric acid and 20 g of potassium permanganate are added.

[0017] Preferably, the modification treatment scheme of basalt fiber is as follows: Step one: the above prepared graphene oxide with different degrees of oxidation is ultrasonically dispersed in water for 150 s. Step two: the basalt fiber is added to the above aqueous solution containing graphene oxide and ultrasonically dispersed for 120 s. Step three: the solution is treated in a constant temperature water bath, the temperature is kept at 30-45°C, and the treatment time is 12 h. Step four: after the constant temperature water bath, ultrasonic dispersion treatment is continued for 30 min, and then the treated basalt fiber is placed in a 100°C oven for drying treatment, and finally the modified basalt fiber is obtained.

[0018] Preferably, in the modification treatment scheme, the graphene oxide is ultrasonically dispersed in water for 150 s.

[0019] Preferably, in the modification treatment scheme, the basalt fiber is ultrasonically dispersed in the graphene aqueous solution for 120s.

[0020] Preferably, in the modification treatment scheme, the final drying temperature of the basalt fiber is 100 DEG C.

[0021] Preferably, the bio-agent loading scheme is as follows: step one, a certain amount of polyvinyl alcohol is placed in distilled water and completely dissolved at 100 DEG C. Step two, the above solution is added to a 2% sodium alginate solution, mixed uniformly, and then the modified basalt fiber is added and mixed uniformly. Step three, after the solution is cooled to 40 DEG C, it is mixed uniformly with the bacteria solution in the logarithmic growth phase at a volume ratio of 5:1, a certain mass fraction of CaCl2 solution is taken with a dropper and added, slightly stirred for 10 min, then the immobilized basalt fiber is taken out, washed with normal saline and dried for use.

[0022] Preferably, in the bio-agent loading scheme, the bio-agent selected is in the logarithmic growth phase

[0023] Preferably, in the bio-agent loading scheme, the concentration of the sodium alginate solution is 2%.

[0024] Preferably, in the bio-agent loading scheme, the mass fraction of CaCl2 is 5%.

[0025] Preferably, in the bio-agent loading scheme, the slight stirring time is 10 min.

[0026] Preferably, the adsorbent fixing scheme is as follows: biomass activated carbon or oxidized biomass activated carbon is deposited and coated on the surface of GO modified basalt fiber with polyurethane emulsion as the sizing agent.

[0027] The present application has the advantages that: the graphene oxide modified basalt is used as a carrier to immobilize the composite microbial agent, supplemented with adsorbents, slow-release carbon sources, etc., which greatly overcomes the defects and restrictions of single treatment agent in treating complex black and odorous water bodies, simplifies the treatment process of black and odorous water bodies, and multiple agents play a role at the same time to achieve excellent treatment effect.

[0028] The advantages of the additional aspects of the present application will be more apparent from the following description section or understood through the practice of the present application. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments description. Obviously, the drawings in the following description only some of the embodiments of the present application, and for those skilled in the art, other drawings can also be obtained from these drawings without creative labor.

[0030] Figure 1 The scanning electron microscope image of the bamboo charcoal described in the embodiments of the present application.

[0031] Figure 2 The scanning electron microscope image of the oxidized bamboo charcoal described in the embodiments of the present application.

[0032] Figure 3 The scanning electron microscope image of the graphene oxide described in the embodiments of the present application. DETAILED DESCRIPTION

[0033] The embodiments of the present application will be described in detail below, and the examples of the embodiments are shown in the drawings, wherein the same or similar notations represent the same or similar elements or elements having the same or similar functions throughout. The embodiments described below through the drawings are exemplary and are only used to explain the present application, and cannot be interpreted as a limitation on the present application.

[0034] Those skilled in the art can understand that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by those skilled in the art to which the present application belongs.

[0035] It should also be understood that terms such as those defined in a general dictionary should be understood to have meanings consistent with those in the context of the prior art, and should not be interpreted with idealized or overly formal meanings unless defined as such.

[0036] Those skilled in the art can understand that, unless otherwise stated, the singular forms "a", "an" and "the" used herein also include the plural forms. It should be further understood that the phrase "comprising" used in the specification of the present application means that the features, integers, steps, operations, elements and / or groups exist, but does not exclude the presence or addition of one or more other features, integers, steps, operations, elements and / or groups thereof.

[0037] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, the person skilled in the art can combine and combine the different embodiments or examples described in the specification and the features of the different embodiments or examples without contradiction.

[0038] In order to facilitate the understanding of the present application, the present application will be further explained and described below with specific embodiments in conjunction with the accompanying drawings, and the specific embodiments do not constitute limitations on the embodiments of the present application.

[0039] The person skilled in the art should understand that the drawings are only schematic diagrams of the embodiments, and the components in the drawings are not necessarily necessary for the implementation of the present application.

[0040] The present application provides a new type of efficient black and odorous water composite treatment and repair agent, which integrates biological, chemical and physical treatment mechanisms. The natural basalt fiber is modified by graphene oxide with different oxidation degrees, and the modified basalt fiber is used as a load fixed carrier to load biological agents, adsorbents and slow-release carbon sources, etc. The defects of single treatment agent in treating black and odorous water are overcome to a great extent.

[0041] The present application integrates biological, physical and chemical treatment. The natural basalt fiber is modified by graphene oxide with different oxidation degrees, and the modified basalt fiber is used as a fixed carrier. Certain biological agents, adsorbents, slow-release carbon sources, etc. are fixed to support the comprehensive treatment and repair agent for black and odorous water.

[0042] Basalt fiber itself is a friendly material, and its large specific surface area provides good mass transfer conditions and oxygen diffusion conditions. Such characteristics can be applied in water treatment as an attachment carrier for microbial growth, but the surface of the untreated basalt fiber will exhibit a certain hydrophobic state, which will affect its affinity and adsorption function in water. After modification by graphene oxide, the graphene oxide surface contains a large number of active oxygen-containing functional groups, which can improve the roughness of the fiber surface after being added to the surface of the basalt fiber, thereby further increasing the specific surface area of the fiber and increasing the number of active functional groups on the surface of the fiber. These functional groups can improve the wettability with water and greatly improve the hydrophobic state of the untreated fiber surface. The number of oxygen-containing functional groups on the surface of graphene oxide with different oxidation degrees is different, so the modified basalt fiber has different affinity and is suitable for different characteristics of black and odorous water.

[0043] The loaded biological agent is mainly composed of bacillus, yeast, photosynthetic bacteria, actinomycetes, nitrifying bacteria, nitrosobacteria and lactic acid bacteria. The loaded multiple biological agents have multiple advantages in water treatment: strong reproduction ability, no harsh requirements for external environmental conditions, simple operation, no secondary pollution, high safety, can adsorb and degrade most pollutants in water, and harmful substances in wastewater can be converted into harmless substances under the action of biological method. In order to avoid the different organic matters in the treatment process, the present application takes sodium alginate as a standby slow-release carbon source.

[0044] The present application adopts biomass activated carbon or oxidized biomass activated carbon as adsorbent, and is loaded on the surface of modified basalt fiber by coating method. The adsorption of heavy metals in water treatment mainly includes physical adsorption and chemical adsorption. The biomass carbon mainly completes the adsorption of heavy metals through physical adsorption, that is, through intermolecular forces. They themselves have developed voids and large specific surface area, so the contact area with metal ions in water is large, and the adsorption performance is excellent. Taking biomass activated carbon or oxidized biomass activated carbon as adsorbent can remove the "black" and "smell" of black and odorous water body. In addition, the biomass activated carbon itself can also serve as a slow-release carbon source, can adhere to and promote the growth of microorganisms, and at the same time avoid the secondary pollution risk caused by external organic carbon source. And after the oxidation treatment, the specific surface area of the biomass carbon is greatly increased, and the surface is rich in oxygen-containing functional groups, which has stronger affinity with water and is easier to adsorb organic pollutants and ionic pollutants.

[0045] Example 1

[0046] The present application provides a preparation method of a black and odorous water body composite treatment and repair agent, comprising the following steps:

[0047] 1) First, the preparation of graphene oxide (GO) with different oxidation degrees is carried out, including

[0048] Step one: weigh 1.5g of natural graphite powder and a certain amount of 98% concentrated sulfuric acid, add to a three-necked flask, place the flask in an ice water bath, and carry out sufficient stirring reaction by mechanical stirring.

[0049] Step two: under stirring condition, a certain amount of potassium permanganate powder is slowly added to the three-necked flask, the reaction temperature is controlled at about 15℃, when there is no purple gas, the stirring reaction is continued at room temperature for 2h, and then it is left overnight.

[0050] Step three: add 100ml deionized water into the three-port flask, control the reaction temperature at about 95℃, continue stirring for 30min, then add 30% H2O2 until the reaction system does not produce bubbles, filter while hot.

[0051] Step four: wash the filter residue with deionized water until the supernatant is neutral, and the filter residue is GO paste.

[0052] The amount of 98% sulfuric acid in step one and the amount of potassium permanganate powder in step two can control the oxidation degree of graphene; 20mL of 98% sulfuric acid is added in step one, and 10g of potassium permanganate powder is added in step two, and the GO prepared by the above steps one to four is light oxidation GO; 100mL of 98% sulfuric acid is added in step one, and 20g of potassium permanganate powder is added in step two, and the GO prepared by the above steps one to four is heavy oxidation GO.

[0053] 2) The modification of basalt fibers using the above different oxidation degrees of graphene oxide:

[0054] Step one: take 2g of the above prepared GO paste of different oxidation degrees, respectively, and place them in 100mL deionized water, and apply ultrasonic cleaner for ultrasonic dispersion, and the treatment time is 10min, to obtain GO dispersion liquid of different oxidation degrees.

[0055] Step two: take 100g of basalt fibers and add them to the above GO dispersion liquid of different oxidation degrees, and continue ultrasonic treatment for 20min.

[0056] Step three: place the above GO and basalt fiber mixture of different oxidation degrees in a 45℃ constant temperature water bath and stand overnight.

[0057] Step four: ultrasonic treat the above GO and basalt fiber mixture of different oxidation degrees which has been standing overnight for 30min, and then filter and dry the residue naturally, to obtain GO modified basalt fibers of different oxidation degrees.

[0058] A small amount of polyurethane emulsion is used as a sizing agent to coat biomass activated carbon or oxidized biomass activated carbon on the surface of basalt fibers modified by graphene oxide of different oxidation degrees.

[0059] 3) The immobilization scheme of biological agent is as follows:

[0060] Step one: take a certain amount of polyvinyl alcohol (degree of polymerization 1800) and place it in distilled water, and completely dissolve it at 100℃.

[0061] Step two: add the above solution to a 2% sodium alginate solution, mix well, and then add the modified basalt fiber and mix well.

[0062] Step three: after the solution is cooled to 40℃, mix it with the bacteria solution in the logarithmic growth phase at a volume ratio of 5:1, use a dropper to add a certain mass fraction (5%) of CaCl2 solution, stir gently for 10 min, then take out the modified basalt fiber fixed with bacteria, wash it with normal saline, dry it, and then use it.

[0063] In this embodiment 1, the slightly oxidized GO modified basalt fiber prepared according to the above technical solution is used as a carrier, and biomass activated carbon is used as an adsorbent. The ratio of basalt fiber, biomass activated carbon, and biological inoculant is 80:10:10. The polyurethane emulsion is used as a sizing agent, the biomass activated carbon is coated on the surface of the slightly oxidized GO modified basalt fiber by coating, the composite inoculant is fixed on the modified basalt fiber carrier coated with biomass activated carbon by using the above biological inoculant loading method, and a black and odorous water composite treatment and repair agent is prepared. This composite treatment and repair agent is suitable for black and odorous water with high organic matter concentration and low ionic pollutant concentration, such as black and odorous water with high organic matter content caused by improper discharge of domestic sewage (dining rooms, civil buildings, etc.). About 10 g of the above black and odorous water composite treatment and repair agent is scattered per square meter of water area, no additional slow-release carbon source is needed, and the effect is better with slight aeration or after the drop or rubber dam.

[0064] In this embodiment 1, the oxidized biomass activated carbon is prepared according to the above technical solution and used as an adsorbent. The heavily oxidized GO modified basalt fiber is prepared according to the above technical solution and used as a carrier. The ratio of basalt fiber, oxidized biomass activated carbon, and biological inoculant is 80:10:10. The polyurethane emulsion is used as a sizing agent, the oxidized biomass activated carbon is coated on the surface of the heavily oxidized GO modified basalt fiber by coating, the composite inoculant is fixed on the modified basalt fiber carrier coated with biomass activated carbon by using the above biological inoculant loading method, and a black and odorous water composite treatment and repair agent is prepared. This composite treatment and repair agent is suitable for black and odorous water with low organic matter concentration and high ionic and heavy metal pollutant concentration, such as black and odorous water caused by improper treatment of industrial wastewater (pharmaceutical, steel, non-ferrous metal, etc.). About 10 g of the above black and odorous water composite treatment and repair agent is scattered per square meter of water area, and if necessary, the effect is better with additional slow-release carbon source sodium alginate.

[0065] Embodiment 2

[0066] In this embodiment 2, a new type of efficient composite black and odorous water treatment and repair agent integrating biological, physical and chemical treatment is provided, which is achieved by the following scheme: adapting biological agent, adsorbent, slow-release carbon source, carrier and the like as main components of the composite black and odorous water treatment and repair agent, and loading and fixing the above components on the adapted carrier by certain technical means, so as to prepare a composite black and odorous water treatment and repair agent integrating biological, physical and chemical repair.

[0067] Specifically, the composite black and odorous water treatment and repair agent described in this embodiment 2 is prepared by the following method: graphene oxide (GO) with different oxidation degrees is selected to modify natural basalt fibers, and the modified basalt fibers are used as the loading and fixing carrier. The fixed microbial agent is composed of bacillus, yeast, photosynthetic bacteria, actinomycetes, nitrifying bacteria, nitrosobacteria and lactic acid bacteria, which mainly degrades and removes nitrogen and phosphorus in black and odorous water. In order to avoid the lack of carbon source during the treatment process, sodium alginate is used as an alternative slow-release carbon source in this scheme. At the same time, basalt fibers have high density and are easy to settle, so the adsorbent is coated on the surface of the modified basalt fibers in this scheme to realize the combined action of adsorption and settlement. Due to the characteristics of wide source, low price and excellent adsorption performance of biomass activated carbon, biomass activated carbon and oxidized biomass activated carbon are used as adsorbents, which are mainly used to remove black, odorous, trace persistent organic pollutants and trace heavy metal pollutants in black and odorous water.

[0068] In this embodiment 2, the preparation scheme of GO with different oxidation degrees is as follows: step one, natural graphite powder and a certain amount of 98% concentrated sulfuric acid are added to a three-necked flask, the flask is placed in an ice water bath, and stirring is carried out; step two, a certain amount of potassium permanganate powder is slowly added to the three-necked flask under stirring, and when no purple gas is emitted, the reaction is continued under room temperature stirring, and then it is left overnight; step three, deionized water is added to the three-necked flask, and stirring is continued, and then H2O2 is added until no bubbles are generated in the reaction system, and it is filtered while hot; step four, the filter residue is washed with deionized water until the supernatant is neutral, and the filter residue is the graphene oxide GO paste.

[0069] Further, the specific steps for preparing GO with different oxidation degrees in this embodiment are as follows: Step one: 1.5 g of natural graphite powder and a certain amount of 98% concentrated sulfuric acid are weighed and added to a three-necked flask, the flask is placed in an ice water bath, and mechanical stirring is adopted for full stirring reaction. Step two: a certain amount of potassium permanganate powder is slowly added to the three-necked flask under stirring, the reaction temperature is controlled at about 15°C, when no purple gas is emitted, the stirring reaction is continued at room temperature for 2 h, and then it is left overnight. Step three: 100 ml of deionized water is added to the three-necked flask, the reaction temperature is controlled at about 95°C, and the stirring is continued for 30 min, then 30% H2O2 is added until no bubbles are generated in the reaction system, and it is filtered while hot. Step four: the filter residue is washed with deionized water until the supernatant is neutral, and the filter residue is GO paste.

[0070] The addition amount of 98% concentrated sulfuric acid in step one and potassium permanganate powder in step two can control the oxidation degree of graphene; 20 mL of 98% concentrated sulfuric acid is added in step one, and 10 g of potassium permanganate powder is added in step two, and the GO prepared through the above steps one to four is light oxidation GO; 100 mL of 98% concentrated sulfuric acid is added in step one, and 20 g of potassium permanganate powder is added in step two, and the GO prepared through the above steps one to four is heavy oxidation GO.

[0071] The above steps one to four can also be used to prepare oxidized biomass activated carbon. The biomass activated carbon is used to replace the natural graphite in step one. Since the biomass activated carbon is more difficult to be oxidized, 75 mL of 98% concentrated sulfuric acid is added in step one, and 12 g of potassium permanganate powder is added in step two, and the oxidized biomass activated carbon is prepared through the above steps one to four.

[0072] In this embodiment 2, the preparation scheme of basalt fibers modified by GO with different oxidation degrees is as follows: Step one: the prepared GO with different degrees of oxidation is dispersed in water by ultrasonic; Step two: the basalt fibers are added to the above water solution containing GO and continue to be treated by ultrasonic dispersion; Step three: the solution is treated by constant temperature water bath; Step four: after the constant temperature water bath, the basalt fibers after treatment are dried, and finally the modified basalt fibers are obtained.

[0073] Further, the preparation steps of the basalt fibers modified by GOs with different oxidation degrees in the embodiment are as follows: step one: 2 g of the prepared GOs with different oxidation degrees is weighed and placed in 100 mL of deionized water, and is subjected to ultrasonic dispersion by using an ultrasonic cleaner for 10 min, to obtain a GO dispersion liquid with different oxidation degrees. Step two: 100 g of basalt fibers is weighed and added into the GO dispersion liquid with different oxidation degrees, and is subjected to ultrasonic treatment for 20 min. Step three: the mixture of the GOs with different oxidation degrees and the basalt fibers is placed in a 45℃ constant-temperature water bath and is left overnight. Step four: the mixture of the GOs with different oxidation degrees and the basalt fibers left overnight is subjected to ultrasonic treatment for 30 min, is filtered, and the residue is naturally dried, to obtain basalt fibers modified by GOs with different oxidation degrees.

[0074] In the embodiment, a small amount of polyurethane emulsion is used as a sizing agent, and biomass activated carbon or oxidized biomass activated carbon is deposited and coated on the surface of the basalt fibers modified by GOs with different oxidation degrees.

[0075] In the embodiment, the bio-agent loading scheme is as follows:

[0076] Step one: a certain amount of polyvinyl alcohol (with a polymerization degree of 1800) is placed in distilled water and is completely dissolved at 100℃.

[0077] Step two: the solution is added into a 2% sodium alginate solution, is uniformly mixed, and then the modified basalt fibers are added and are uniformly mixed.

[0078] Step three: after the solution is cooled to 40℃, the solution is uniformly mixed with a bacterial solution in the logarithmic growth phase at a volume ratio of 5:1, a certain mass fraction (5%) of a CaCl2 solution is dropped into the solution by using a dropper, and is slightly stirred for 10 min, then the modified basalt fibers with the bacteria are taken out, are washed clean with normal saline, are dried, and are ready for use.

[0079] Meanwhile, in order to avoid the situation of insufficient carbon source during the treatment process, sodium alginate is used as a backup slow-release carbon source in the embodiment.

[0080] In this embodiment 2, the slightly oxidized GO modified basalt fiber prepared according to the above technical solution is used as a carrier, and the biomass activated carbon is used as an adsorbent. The ratio of basalt fiber, biomass activated carbon and biological agent is 80:10:10. The polyurethane emulsion is used as a sizing agent, the biomass activated carbon is coated on the surface of the slightly oxidized GO modified basalt fiber by coating, the composite microbial agent is fixed on the modified basalt fiber carrier coated with the biomass activated carbon by using the above biological agent loading method, and the black and odorous water composite treatment and repair agent is prepared. The composite treatment and repair agent is suitable for the black and odorous water with high organic matter concentration and low ion type pollutant concentration, for example, the black and odorous water with high organic matter content caused by improper discharge of domestic sewage (dining room, civil building, etc.). About 10 g of the above black and odorous water composite treatment and repair agent is scattered per square meter of water area, no additional slow-release carbon source is needed, and the effect is better with slight aeration or after the drop or rubber dam.

[0081] In this embodiment 2, the slightly oxidized GO modified basalt fiber prepared according to the above technical solution is used as a carrier, and the biomass activated carbon is used as an adsorbent. The ratio of basalt fiber, biomass activated carbon and biological agent is 80:10:10. The polyurethane emulsion is used as a sizing agent, the biomass activated carbon is coated on the surface of the slightly oxidized GO modified basalt fiber by coating, the composite microbial agent is fixed on the modified basalt fiber carrier coated with the biomass activated carbon by using the above biological agent loading method, and the black and odorous water composite treatment and repair agent is prepared. The composite treatment and repair agent is suitable for the black and odorous water with high organic matter concentration and low ion type pollutant concentration, for example, the black and odorous water with high organic matter content caused by improper discharge of domestic sewage (dining room, civil building, etc.). About 10 g of the above black and odorous water composite treatment and repair agent is scattered per square meter of water area, no additional slow-release carbon source is needed, and the effect is better with slight aeration or after the drop or rubber dam.

[0082] As shown in Tables 1 and 2, the natural basalt fiber used in the black and odorous water composite treatment and repair agent has the characteristics of environmental friendliness, large density and easy settlement. Because the specific surface area is large and the mass transfer and oxygen diffusion conditions are good, the basalt fiber acts as a carrier and an adsorbent in the black and odorous water composite treatment and repair agent. The parameters after the repair of the black and odorous water using the repair agent prepared in embodiments 1 and 2 and the parameters after the repair of the black and odorous water using a single method are compared as shown in Tables 1 and 2.

[0083] Table 1

[0084]

[0085] Table 2

[0086]

[0087] After basalt fibers are modified by GOs with different oxidation degrees, the roughness of the surface of the basalt fibers is increased, and the surface area of the basalt fibers is increased, and the number of oxygen-containing functional groups on the surface of the GOs with different oxidation degrees is different, so that the GO-modified basalt fibers have different affinity, which is suitable for different black and odorous water bodies. For example, the GO-modified basalt fibers with mild oxidation are more suitable for black and odorous water bodies with high concentrations of organic pollutants, especially persistent organic pollutants, when combined with biomass activated carbon; the GO-modified basalt fibers with severe oxidation are more suitable for black and odorous water bodies with high concentrations of ionic pollutants, especially high-polarity organic pollutants or heavy metal pollutants, when combined with oxidized biomass activated carbon.

[0088] Loading various adapted biological agents in the treatment of black and odorous water bodies has many advantages, such as strong reproductive ability, no harsh requirements for habitat environment, promoting the degradation of most pollutants in water, etc. At the same time, biological agents are easy to operate, do not produce secondary pollution, have high safety, low cost, and strong sustainability. Biomass activated carbon not only has strong adsorption, but also has the function of slow-release carbon source, can attach, enrich and promote the growth of microorganisms, promote nitrification, and at the same time avoid the risk of secondary pollution caused by the addition of organic carbon source. Oxidized biomass activated carbon has a larger surface area than biomass activated carbon, and is rich in oxygen-containing functional groups on the surface, has stronger affinity with water, and is more easily adsorbed by polar organic pollutants and ionic pollutants (such as antibiotics, heavy metals, etc.).

[0089] Although the specific embodiments of the present application are described above in combination with the accompanying drawings, it is not a limitation on the scope of protection of the present application. Those skilled in the art should understand that various modifications or variations made by those skilled in the art on the basis of the technical solutions disclosed in the present application without creative labor should be covered within the scope of protection of the present application.

Claims

1. A method for preparing a composite treatment and remediation agent for black and odorous water bodies, characterized in that, A suitable biological agent, adsorbent, and slow-release carbon source are loaded or immobilized on a suitable carrier; wherein, the biological agent is a mixed agent including Bacillus, photosynthetic bacteria, actinomycetes, nitrifying bacteria, and lactic acid bacteria; the adsorbent is biomass activated carbon or oxidized biomass activated carbon; the suitable carrier is basalt fiber modified with graphene oxide to different degrees of oxidation; wherein, the preparation of graphene oxide to different degrees of oxidation includes: Step 1: Take natural graphite powder and a certain amount of 98% concentrated sulfuric acid, add them to a three-necked flask, place the flask in an ice-water bath, and stir the reaction. Step 2: Under stirring, slowly add a certain amount of potassium permanganate powder to the three-necked flask. When no purple gas is emitted, continue stirring the reaction at room temperature, and then let it stand overnight. Step 3: Add deionized water to the three-necked flask, continue stirring, and then add H2O2 until no more bubbles are produced in the reaction system. Filter while hot. Step 4: Wash the filter residue with deionized water until the supernatant is neutral. The filter residue is the viscous substance of graphene oxide (GO). The modification treatment of basalt fiber includes: Step 1, ultrasonically dispersing the prepared graphene oxide of different degrees in water; Step 2, adding the basalt fiber to the above-mentioned aqueous solution containing graphene oxide and continuing ultrasonic dispersion treatment; Step 3, treating the solution in a constant temperature water bath; Step 4, continuing ultrasonic dispersion treatment after the constant temperature water bath, drying the treated basalt fiber, and finally obtaining the modified basalt fiber. The loading of the biological agent includes: Step 1: Dissolve a certain mass of polyvinyl alcohol in distilled water at 100℃; Step 2: Add the above solution to a 2% sodium alginate solution, mix well, and then add the modified basalt fiber and mix well; Step 3: After cooling the solution to 40℃, mix it with the bacterial solution in the logarithmic growth phase at a volume ratio of 5:1, add a certain mass fraction of CaCl2 solution dropwise, stir gently for 10 minutes, then take out the immobilized basalt fiber, wash it with physiological saline, and dry it for later use.

2. The method for preparing the composite treatment and remediation agent for black and odorous water bodies according to claim 1, characterized in that, Step 1: Take 1.5g of natural graphite powder and a certain amount of 98% concentrated sulfuric acid. Step 2: Under stirring conditions, slowly add a certain amount of potassium permanganate powder into a three-necked flask, control the reaction temperature at 15℃, and continue stirring the reaction for 2 hours at room temperature when no purple gas is emitted.

3. The method for preparing the composite treatment and remediation agent for black and odorous water bodies according to claim 2, characterized in that, In step three, add 100 ml of deionized water to the three-necked flask, control the reaction temperature at 95°C, stir continuously for 30 min, and then add 30% H2O2.

4. The method for preparing the composite treatment and remediation agent for black and odorous water bodies according to claim 2, characterized in that, The amount of concentrated sulfuric acid added was 200 ml, and the amount of potassium permanganate added was 5 g.

5. The method for preparing the composite treatment and remediation agent for black and odorous water bodies according to claim 2, characterized in that, The amount of concentrated sulfuric acid added was 100 ml, and the amount of potassium permanganate added was 20 g.

6. The method for preparing the composite treatment and remediation agent for black and odorous water bodies according to claim 1, characterized in that, Step 1: The prepared graphene oxide of different degrees was ultrasonically dispersed in water for 150 seconds. Step 2: Basalt fibers were added to the above aqueous solution containing graphene oxide and ultrasonically dispersed for 120 seconds. Step 3: The solution was subjected to a constant temperature water bath treatment at 30-45°C for 12 hours. Step 4: After the constant temperature water bath, ultrasonic dispersion was continued for 30 minutes. Finally, the treated basalt fibers were dried at 100°C to obtain the modified basalt fibers.

7. The method for preparing the composite treatment and remediation agent for black and odorous water bodies according to claim 1, characterized in that, The fixation of the adsorbent includes: using polyurethane emulsion as a sizing agent, depositing and coating biomass activated carbon or oxidized biomass activated carbon onto the surface of GO modified basalt fibers with different oxidation levels.

Images