阅读说明：本技术 一种含有化学除磷药剂的生物质碳源及其制备方法和应用 (Biomass carbon source containing chemical phosphorus removal agent and preparation method and application thereof ) 是由 兰华春 安晓强 苗时雨 刘会娟 曲久辉 于 2021-07-21 设计创作，主要内容包括：本发明属于污水生化处理技术领域,具体涉及一种含有化学除磷药剂的生物质碳源及其制备方法和应用。所述制备方法包括如下步骤：对生物质溶液进行再处理,破除生物质分子间氢键作用后,添加水溶性高分子聚合物,第一搅拌后,添加化学除磷药剂,第二搅拌,得含有化学除磷药剂的生物质碳源。上述方法制备得到的含有化学除磷药剂的生物质碳源主要用于强化生物反硝化脱氮的同时去除水中的有机磷和无机磷,操作简单,所需设备少,能耗低,无需特殊高温高压装置即可实现对分子结构的调控,方法普适性好。(The invention belongs to the technical field of biochemical sewage treatment, and particularly relates to a biomass carbon source containing a chemical phosphorus removal agent, and a preparation method and application thereof. The preparation method comprises the following steps: and (3) reprocessing the biomass solution, breaking the hydrogen bond action among the biomass molecules, adding a water-soluble high polymer, adding a chemical phosphorus removal agent after the first stirring, and stirring the mixture for the second time to obtain the biomass carbon source containing the chemical phosphorus removal agent. The biomass carbon source containing the chemical phosphorus removal agent prepared by the method is mainly used for removing organic phosphorus and inorganic phosphorus in water while enhancing biological denitrification, is simple to operate, requires less equipment, is low in energy consumption, can realize regulation and control of a molecular structure without a special high-temperature high-pressure device, and is good in universality.)

1. A preparation method of a biomass carbon source containing a chemical phosphorus removal agent comprises the following steps:

and (3) reprocessing the biomass solution, breaking the hydrogen bond action among the biomass molecules, adding a water-soluble high polymer, adding a chemical phosphorus removal agent after the first stirring, and stirring the mixture for the second time to obtain the biomass carbon source containing the chemical phosphorus removal agent.

2. The production method according to claim 1,

the biomass solution is a biomass product or is obtained by pretreating the biomass product;

wherein the pretreatment comprises the steps of adding an alkali reagent into a biomass product, reacting, separating and removing impurities;

the biomass product comprises at least one of anaerobic fermentation products of excess sludge of municipal sewage plants, oil processing byproducts, wastewater discharged by breweries and wastewater discharged by starch plants.

3. The production method according to claim 1,

the chemical phosphorus removal agent comprises at least one of iron-containing metal salt, aluminum-containing metal salt, zirconium-containing metal salt or lanthanum-containing metal salt;

the concentration of the chemical phosphorus removal agent in the biomass solution is 0.001-0.5 mol/L;

preferably, the concentration of the chemical phosphorus removal agent in the biomass solution is 0.03 mol/L.

4. The production method according to claim 1 or 2,

the reprocessing comprises at least one of heating, adding acid, adding water, third stirring, microwave and ultrasound.

5. The production method according to claim 4,

the heating is carried out at 50-100 ℃ and the stirring is carried out for 2-24 hours;

the acid adding is to add an acid reagent into the biomass solution and stir for 2-24 hours; wherein the volume ratio of the biomass solution to the acid reagent is 1: 0.005-0.3;

the third stirring time is 1-4 hours;

the microwave time is 1-20 minutes; preferably, the microwave time is 1-10 minutes;

the ultrasonic time is 5-30 minutes.

6. The production method according to claim 1,

the water-soluble high molecular polymer comprises at least one of glucose, amino acid, polyacrylic acid, polyethylene glycol, polyglutamic acid, polycysteine, polyaspartic acid and polyethyleneimine;

preferably, the volume ratio of the biomass solution to the water-soluble high molecular polymer is 1: 0.0001-1: 0.05.

7. the production method according to claim 2,

during the pretreatment:

the mass ratio of the biomass product to the alkali reagent is 1 (1-5); adding an alkali reagent until the pH value of the system is 7-12; the reaction time is 2-12 hours;

the alkali reagent comprises at least one of potassium hydroxide and sodium hydroxide;

and the separation and impurity removal comprises at least one of standing, precipitation, separation and impurity removal or centrifugal separation and impurity removal.

8. The biomass carbon source containing the chemical phosphorus removal agent prepared by the preparation method of any one of claims 1 to 7.

9. The use of the biomass carbon source containing chemical phosphorus removal agents as claimed in claim 8 for enhanced biological denitrification and simultaneous phosphorus removal.

10. Use according to claim 9, comprising the steps of:

under the anaerobic condition, adding a biomass carbon source containing a chemical phosphorus removal agent into an activated sludge solution cultured with denitrifying microorganisms, stirring, introducing waste liquid simultaneously containing nitrate, inorganic phosphate and organic phosphorus, and treating to realize enhanced denitrifying denitrification of the biomass carbon source and synergistic removal of the inorganic phosphorus and the organic phosphorus through chemical action.

Preferably; the time of denitrification treatment is 2-6 hours;

the concentration of the sludge in the activated sludge solution is 1000-10000 mg/L;

the molar ratio of carbon provided by the biomass carbon source to nitrogen in the nitrate to phosphorus provided by the inorganic phosphate to the organic phosphorus is (3-10) to 1 (0.1-5).

Technical Field

The invention belongs to the technical field of biochemical sewage treatment, and particularly relates to a biomass carbon source containing a chemical phosphorus removal agent, and a preparation method and application thereof.

Background

With the rapid development of economic society, water resource shortage and water eutrophication become outstanding environmental problems restricting human health and social sustainable development. The key of water eutrophication treatment lies in the removal of nitrogen and phosphorus, and the important function is played in realizing water restoration by the nitrogen and phosphorus removal function of denitrifying bacteria and phosphorus accumulating bacteria based on the microbiological principle, and the application of the water eutrophication treatment in a sewage process is more and more extensive based on the application of the water eutrophication treatment.

The restoration technology is one of effective ways for solving the eutrophication of the water body. However, in the traditional biological nitrogen and phosphorus removal process, nitrogen and phosphorus removal efficiency is not high due to problems of carbon source competition, non-uniform sludge age adaptation and the like between denitrifying bacteria and phosphorus accumulating bacteria, so that the effluent quality is influenced to reach the standard.

The chemical phosphorus removal has the characteristics of high removal rate, stable treatment effect and the like. The performance of the biological denitrification synchronous chemical phosphorus removal efficiency depends on the added chemical substances and the synergistic action process between the chemical substances and the microorganisms. In particular, a large amount of organic substances are consumed in the microbial denitrification process as electron donors, and synthetic compounds such as glucose, sodium acetate and the like are added in the actual process to realize the denitrification. These artificial chemicals are expensive, and the synthesis process faces problems of additional energy consumption and pollutant emissions. In addition, the former development of the denitrification organic carbon source only focuses on the capability of the denitrification organic carbon source to be absorbed and utilized by microorganisms, and the role of the denitrification organic carbon source in removing phosphorus-containing substances is yet to be excavated.

Disclosure of Invention

The invention provides a method for modifying a biomass carbon source based on a biomass intermolecular hydrogen bond acting force regulation and control principle, the modification method is simple and easy to control, the applicability is strong, the bioavailability of the obtained carbon source is good, and an effective way is provided for the efficient resource utilization of waste biomass.

The invention provides a preparation method of a biomass carbon source containing a chemical phosphorus removal agent, which comprises the following steps:

and (3) reprocessing the biomass solution, breaking the hydrogen bond action among the biomass molecules, adding a water-soluble high polymer, adding a chemical phosphorus removal agent after the first stirring, and stirring the mixture for the second time to obtain the biomass carbon source containing the chemical phosphorus removal agent.

Further, the biomass solution is a biomass product or is obtained by pretreating the biomass product;

wherein the pretreatment comprises the steps of adding an alkali reagent into a biomass product, reacting, separating and removing impurities;

the biomass product comprises at least one of anaerobic fermentation products of excess sludge of municipal sewage plants, oil processing byproducts, wastewater discharged by breweries and wastewater discharged by starch plants.

Further, the chemical phosphorus removal agent comprises at least one of iron-containing metal salt, aluminum-containing metal salt, zirconium-containing metal salt or lanthanum-containing metal salt;

the concentration of the chemical phosphorus removal agent in the biomass solution is 0.001-0.5 mol/L;

preferably, the concentration of the chemical phosphorus removal agent in the biomass solution is 0.03 mol/L.

Further, the reprocessing comprises at least one of heating, adding acid, adding water, third stirring, microwave and ultrasound.

Further, the heating is carried out at 50-100 ℃ for 2-24 hours;

the acid adding is to add an acid reagent into the biomass solution and stir for 2-24 hours; wherein the volume ratio of the biomass solution to the acid reagent is 1: 0.005-0.3;

the third stirring time is 1-4 hours;

the microwave time is 1-20 minutes; preferably, the microwave time is 1-10 minutes;

the ultrasonic time is 5-30 minutes.

Further, the water-soluble high molecular polymer comprises at least one of glucose, amino acid, polyacrylic acid, polyethylene glycol, polyglutamic acid, polycysteine, polyaspartic acid and polyethyleneimine;

preferably, the volume ratio of the biomass solution to the water-soluble high molecular polymer is 1: 0.0001-1: 0.05.

further, the pretreatment is as follows:

the mass ratio of the biomass product to the alkali reagent is 1 (1-5); adding an alkali reagent until the pH value of the system is 7-12; the reaction time is 2-12 hours;

the alkali reagent comprises at least one of potassium hydroxide and sodium hydroxide;

and the separation and impurity removal comprises at least one of standing, precipitation, separation and impurity removal or centrifugal separation and impurity removal.

The invention also provides a biomass carbon source containing the chemical phosphorus removal agent, which is prepared by any preparation method.

The invention also provides application of any biomass carbon source containing the chemical phosphorus removal agent in enhanced biological denitrification nitrogen removal and synchronous phosphorus removal.

Further, the method comprises the following steps:

under the anaerobic condition, adding a biomass carbon source containing a chemical phosphorus removal agent into an activated sludge solution cultured with denitrifying microorganisms, stirring, introducing waste liquid simultaneously containing nitrate, inorganic phosphate and organic phosphorus, and treating to realize enhanced denitrifying denitrification of the biomass carbon source and synergistic removal of the inorganic phosphorus and the organic phosphorus through chemical action.

Preferably; the time of denitrification treatment is 2-6 hours;

the concentration of the sludge in the activated sludge solution is 1000-10000 mg/L;

the molar ratio of carbon provided by the biomass carbon source to nitrogen in the nitrate to phosphorus provided by the inorganic phosphate to the organic phosphorus is (3-10) to 1 (0.1-5).

The invention has the following advantages:

the preparation method of the biomass carbon source provided by the invention selects waste biomass products as raw materials, regulates and controls the intermolecular hydrogen bonding action of the biomass by adding water for dilution, acidity regulation, heating, stirring, microwave, ultrasound and other modes, breaks part of the intermolecular hydrogen bonding action of the biomass, then adds water-soluble high molecular polymer with good biocompatibility and water solubility, reduces the intermolecular hydrogen bonding aggregation action by means of a polymer skeleton structure, and simultaneously, functional groups such as hydroxyl, amino, carboxyl and the like contained in the polymer can provide necessary conditions for forming new hydrogen bonding action with the biomolecule, thereby finally improving the biological absorption and utilization degree of the carbon source. And moreover, a chemical phosphorus removal agent is added, so that the synchronous removal of nitrogen and phosphorus can be realized.

The preparation method of the biomass carbon source provided by the invention is simple to operate, requires less equipment, is low in energy consumption, can realize regulation and control of the molecular structure without a special high-temperature high-pressure device, and is good in universality.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:

FIG. 1 is an infrared spectrum of a sample of a by-product of oil and fat processing before and after modification with polyethyleneimine in example 1.

FIG. 2 is an infrared spectrum of a sample of a fat or oil processing by-product before and after modification with polyaspartic acid in example 2.

FIG. 3 is a graph of performance effects of grease processing byproducts and a control group on removal of nitrate by microbial denitrification before and after modification in application example 1.

FIG. 4 is a graph showing the change of nitrite concentration in the process of removing nitrate by microbial denitrification in the starch wastewater and the control before and after modification in application example 2.

FIG. 5 is a graph showing the change of nitrite concentration and total phosphorus concentration in the process of removing nitrate by microbial denitrification in the starch wastewater and the control group before and after modification in application example 3.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The embodiments and features of the embodiments of the present invention may be combined with each other without conflict.

One embodiment of the invention provides a preparation method of a biomass carbon source, which comprises the following steps:

and (3) reprocessing the biomass solution, breaking the hydrogen bond action among the biomass molecules, adding a water-soluble high molecular polymer, and stirring for the first time to obtain the biomass carbon source.

According to the preparation method of the biomass carbon source provided by the embodiment of the invention, waste biomass products are selected as raw materials, the intermolecular hydrogen bonding effect of the biomass is regulated and controlled by adding water for dilution, acid regulation, heating, stirring, microwave, ultrasonic and other modes, then the water-soluble high-molecular polymer with good biocompatibility and water solubility is added, the intermolecular hydrogen bonding aggregation effect is reduced by means of a polymer skeleton structure, meanwhile, functional groups such as hydroxyl, amino, carboxyl and the like contained in the polymer can provide necessary conditions for forming new hydrogen bonding effect with the biomolecule, the biological absorption and utilization degree of the carbon source is effectively improved finally, and the nitrogen removal process is stable in operation.

The preparation method of the biomass carbon source provided by the embodiment of the invention has the advantages of simple operation, less required equipment, low energy consumption, no need of a special high-temperature high-pressure device, capability of realizing regulation and control of a molecular structure and good universality.

Further, a preferred embodiment of the present invention further provides a method for preparing a biomass carbon source containing a chemical phosphorus removal agent, comprising the following steps:

and (2) reprocessing the biomass solution, breaking the hydrogen bond action among the biomass molecules, adding a water-soluble high molecular polymer, carrying out first stirring to obtain a biomass carbon source, adding a chemical phosphorus removal agent, and carrying out second stirring to obtain the biomass carbon source containing the chemical phosphorus removal agent.

According to the embodiment of the invention, the waste biomass is subjected to molecular modification, so that the bioavailability of the waste biomass is improved, the cost of a carbon source is reduced, and the synchronous reinforcement of the microbial denitrification and the chemical phosphorus removal process is realized by virtue of the intermolecular action between the waste biomass and the phosphorus-containing substance. The embodiment of the invention has important significance for developing a low-cost carbon source which can provide a carbon source and strengthen the phosphorus removal function based on waste biomass and further establishing a biological/chemical synergistic nitrogen and phosphorus removal system.

Specifically, firstly, the biomass solution is treated by heating, adding acid, adding water, microwave, ultrasound, and the like, the intermolecular hydrogen bonding action of the biomass solution is partially broken, then a certain amount of water-soluble high polymer is added, various functional groups existing in the substance molecules and the treated biomass molecules form a new valence bond structure, and the polymerization skeleton structure of the substance molecules is utilized as far as possible to reduce the intermolecular strong hydrogen bonding action, so that the purposes of reducing the viscosity, enhancing the dispersibility of the substance in water, promoting the surface attachment of microorganisms, utilizing the organisms and the like are achieved. Adding metal salts containing iron, aluminum, zirconium, lanthanum and the like as chemical inorganic phosphorus removal agents, and performing denitrification treatment on wastewater simultaneously containing nitrate, inorganic phosphate and organic phosphorus under anaerobic conditions by proper stirring to achieve the purposes of enhanced denitrification of modified biomass carbon sources and removal of inorganic phosphorus and organic phosphorus by chemical cooperation.

The method for preparing the modified biomass carbon source with the enhanced nitrogen and phosphorus removal function, provided by the embodiment of the invention, is simple and easy to control, has strong applicability, good bioavailability of the obtained carbon source, and adjustable type of interaction with phosphorus-containing substances, and provides an effective way for efficient resource utilization of waste biomass.

Specifically, the concentration of the chemical phosphorus removal agent in the biomass solution is (0.001-0.5) mmol/L; preferably, the concentration of the chemical phosphorus removal agent in the biomass solution is 0.03 mol/L.

Specifically, the chemical phosphorus removal agent comprises at least one of iron-containing metal salt, aluminum-containing metal salt, zirconium-containing metal salt or lanthanum-containing metal salt. For example, the chemical phosphorus removal agent can be ferric chloride, aluminum chloride, zirconium nitrate, or lanthanum nitrate.

In an embodiment of the present invention, the biomass solution is a biomass product or is obtained by pretreating a biomass product.

Specifically, the biomass product comprises at least one of anaerobic fermentation products of excess sludge of municipal sewage plants, oil processing byproducts, wastewater discharged from breweries and wastewater discharged from starch plants. Wherein the oil processing by-products comprise organic by-products generated in the production of biodiesel and the like. The biomass products all contain high-concentration organic biomass, and can provide a carbon source for denitrifying organisms to realize the application of sewage denitrification.

Preferably, when the biomass product is wastewater discharged from a starch factory, the method further comprises the step of performing acidification treatment on the wastewater discharged from the starch factory, and then performing pretreatment.

Preferably, when the biomass product is wastewater discharged from a brewery, the wastewater discharged from the brewery contains less lipid, and is directly reprocessed without pretreatment, so that the hydrogen bonding effect between biomass molecules is broken.

Preferably, when the biomass product is a grease processing byproduct, sand filtration pretreatment and the like can be directly carried out according to specific components in the grease processing byproduct.

Specifically, the biomass product is obtained by pretreatment, wherein the pretreatment comprises the steps of adding an alkali reagent into the biomass product, reacting, separating and removing impurities. Adding an alkali reagent into the biomass product to promote the reaction of the residual lipid substances in the biomass product to generate fatty acid sodium soap, so as to prevent the interference of the lipid on the subsequent intermolecular modification reaction. By pretreating the biomass product, insoluble fatty acid, lipid, soap, solid suspended matter, etc. remained in the raw material are removed, and organic substances capable of being absorbed by living organisms such as saccharides, small molecular fatty acid, alcohols, etc. are retained.

Preferably, the alkali reagent comprises at least one of potassium hydroxide and sodium hydroxide. The mass ratio of the biomass product to the alkali reagent is 1 (1-5). The alkaline agent may be added in the form of a solution. The concentration of the alkaline agent may be 0.1-5M. For example, it may be added in the form of an aqueous solution of an alkali agent having a concentration of 1M.

Preferably, the alkali agent is added to a system pH of 7-12. So that lipid substances in the biomass product can react to generate the fatty acid sodium soap.

Preferably, the reaction time is 2 to 12 hours. Stirring is carried out during the reaction to promote the raw materials to fully react. Preferably, the separation and impurity removal comprises at least one of standing precipitation separation and impurity removal or centrifugal separation and impurity removal

More preferably, the standing precipitation impurity removal specifically comprises: and standing the pretreated biomass product for more than 12 hours, and taking supernatant as a separated product.

More preferably, the centrifugal separation impurity removal specifically comprises: 2000-10000 rpm, centrifuging for 10-30 minutes, and taking the supernatant as the separated product. More specifically, the centrifugation is performed in a high speed rotary centrifuge.

In the embodiment of the invention, the hydrogen bond action among the biomass molecules is regulated and controlled by adding water for dilution, acidity regulation, heating, stirring, microwave, ultrasound and other modes, part of the hydrogen bond action among the biomass molecules is broken, a premise is provided for fully putting the modified high molecular polymer into the molecules, the solution viscosity can be effectively reduced, and the interaction between the polymer and the biomolecules in the aqueous solution is enhanced.

Specifically, the reprocessing includes at least one of heating, adding acid, adding water, third stirring, microwave, and ultrasound. Preferably, the reprocessing may include one of heating, adding acid, adding water and stirring, adding water and microwaving, adding water and sonicating. For example, an appropriate amount of water may be added to the biomass solution, and the volume ratio of biomass product to water may be 1: 0.1.

preferably, the heating is performed at 50-100 ℃ for 2-24 hours with stirring.

Preferably, the acid is added into the biomass solution, and the mixture is stirred for 2 to 24 hours; wherein the volume ratio of the biomass solution to the acid reagent is 1: 0.001-0.1. The acid reagent comprises at least one of concentrated hydrochloric acid, concentrated sulfuric acid or concentrated nitric acid.

Preferably, the third stirring time is 1 to 4 hours.

Preferably, the microwave time is 1-20 minutes; preferably, the microwave time is 1-10 minutes.

Preferably, the time of the sonication is 5 to 30 minutes. The power of the ultrasonic wave is 200-400W. Preferably, the power of the ultrasound is 300W.

According to the embodiment of the invention, the biomass solution is subjected to retreatment such as heating, acid adding, water adding, third stirring, microwave, ultrasonic treatment and the like, one of the modes can be directly adopted, or the modes can be combined and the like, and can be adjusted according to requirements, so that the hydrogen bond effect among biomass molecules can be broken to different degrees.

In the embodiment of the invention, a water-soluble high molecular polymer with good biocompatibility and water solubility is used as a hydrogen bond regulating and controlling reagent, the aggregation of intermolecular hydrogen bonds is reduced by virtue of the polymer skeleton structure, and meanwhile, functional groups such as hydroxyl, amino, carboxyl and the like contained in the water-soluble high molecular polymer can provide necessary conditions for forming a new hydrogen bond effect with biomolecules, so that the biological absorption and utilization degree of a carbon source is finally improved.

In an embodiment of the present invention, the water-soluble high molecular polymer includes at least one of glucose, amino acid, polyacrylic acid, polyethylene glycol, polyglutamic acid, polycysteine, polyaspartic acid, and polyethyleneimine.

Wherein, the molecular mass of the polyethyleneimine can be 100-10000; the polyethyleneimine may have a molecular mass of 600.

The molecular mass of the polyaspartic acid can be 100-10000; preferably, the polyaspartic acid may have a molecular mass of 1000.

The molecular mass of polyacrylic acid can be 100-10000; preferably, the polyacrylic acid may have a molecular mass of 2000.

Glucose may have a molecular mass of 180;

the amino acid may be cysteine or aspartic acid. For example, cysteine has a molecular weight of 121 and aspartic acid has a molecular weight of 133.

The molecular mass of the polyethylene glycol can be 200-800.

The molecular mass of the polyglutamic acid can be 1 to 10 ten thousand.

The molecular mass of the polycysteine can be 1000-2 ten thousand.

Preferably, the volume ratio of the biomass solution to the water-soluble high molecular polymer is 1: 0.0001-1: 0.05. preferably, the volume ratio of the biomass solution to the water-soluble high molecular polymer is 1: 0.005-1: 0.05.

in one embodiment of the present invention, the first stirring time is 2 to 24 hours. The temperature of the first stirring is 20-80 ℃. Preferably, the temperature of the first stirring may be room temperature. The action between the water-soluble high molecular polymer and the biological molecules is promoted by stirring.

The embodiment of the invention also provides a biomass carbon source prepared by any one of the preparation methods.

The embodiment of the invention also provides application of the biomass carbon source in strengthening biological denitrification and synchronous phosphorus removal. In particular to application of the biomass carbon source in enhancing biological denitrification and denitrification of wastewater. The application comprises the following steps:

adding a biomass carbon source into an activated sludge solution cultured with denitrifying microorganisms under anaerobic conditions, stirring, and introducing a waste liquid containing nitrate to perform denitrification treatment to realize denitrification.

Preferably, the time of the denitrification treatment is 2 to 6 hours. The concentration of the sludge in the activated sludge solution is 1000-10000 mg/L. The molar ratio of carbon provided by the biomass carbon source to nitrogen in the nitrate is 1:1-5: 1. And performing denitrification treatment under anaerobic conditions by applying proper stirring.

An embodiment of the invention also provides a biomass carbon source containing the chemical phosphorus removal agent, which is prepared by any one of the preparation methods.

The embodiment of the invention also provides application of the biomass carbon source containing the chemical phosphorus removal agent in enhanced biological denitrification nitrogen and phosphorus removal. In particular to application of the biomass carbon source containing the chemical phosphorus removal agent in enhancing biological denitrification nitrogen removal and phosphorus removal of wastewater. The phosphorus includes inorganic phosphorus and organic phosphorus. For example, inorganic phosphate may be used.

Specifically, the method comprises the following steps:

under the anaerobic condition, adding a biomass carbon source containing a chemical phosphorus removal agent into an activated sludge solution cultured with denitrifying microorganisms, stirring, introducing waste liquid simultaneously containing nitrate, inorganic phosphate and organic phosphorus, and treating to realize the enhanced denitrification and chemical synergistic removal of inorganic phosphorus and organic phosphorus by the modified biomass carbon source.

Preferably, the treatment time is 2 to 6 hours. The concentration of the sludge in the activated sludge solution is 1000-10000 mg/L. The molar ratio of carbon provided by the biomass carbon source to nitrogen in the nitrate to phosphorus provided by the inorganic phosphate to the organic phosphorus is (3-10) to 1 (0.1-5). And performing denitrification treatment under anaerobic conditions by applying proper stirring.

In the embodiment of the invention, a chemical phosphorus removal agent is added, so that the synchronous removal of nitrogen and phosphorus can be realized. The soluble metal ions can be combined with inorganic phosphorus salt ions and organic phosphorus in the sewage to generate an insoluble compound, thereby providing favorable conditions for the efficient and stable removal of phosphorus-containing substances.

The present invention will be described in detail with reference to examples.

Example 1A preparation method of a microbial carbon source for modifying a grease processing byproduct comprises the following steps:

step 1: and (3) pretreating 40 ml of the oil processing by-product, adjusting the pH value of the solution to 9 by using 1M sodium hydroxide solution, and stirring at room temperature for 3 hours to promote the residual lipid substances in the oil processing by-product raw material to react to generate the fatty acid sodium soap.

Step 2: and (3) separating the solution obtained in the step (1) by adopting a high-speed rotating centrifuge, treating for 15 minutes at the rotating speed of 5000 r/min, and removing the lower-layer precipitate to obtain a product obtained by treatment.

And step 3: taking 10 ml of the separated solution obtained in the step 2, dropwise adding 0.1 ml of concentrated hydrochloric acid at the rotation speed of 300 revolutions per minute, adding 50 microliters of polyethyleneimine (M is 600) and continuing stirring for 10 hours, and collecting the final solution as a microorganism denitrification carbon source.

The infrared spectrum is adopted to analyze the grease processing byproduct samples before and after the modification of the polyethyleneimine, and the result is shown in figure 1. Referring to fig. 1, the a-curve represents the raw grease processing by-product. The c curve represents the fat processing by-product obtained after the heating pretreatment in step 1. And b, representing the oil processing by-product obtained after hydrogen bond modification in the step 3.

From fig. 1, it can be seen that modification of polyethyleneimine can promote hydrogen bond breaking of biomass molecules to reform hydrogen bond structures, so that hydroxyl absorption peaks move to low wave numbers.

Example 2A preparation method of a modified oil processing byproduct microbial carbon source comprises the following steps:

step 1: taking 40 ml of the grease processing by-product, removing non-soluble residual substances in the raw material by sand filtration interception, and collecting the filtrate as a pretreatment product.

Step 2: and (3) taking 10 ml of the pretreated clear liquid, performing microwave treatment for 2 minutes every 2 minutes under the microwave condition, and sequentially repeating the microwave treatment for 10 times to treat the clear liquid so as to regulate the intermolecular hydrogen bond action of the biomass.

And step 3: to the above treatment solution, 50 μ l of polyaspartic acid (M1000) was added, and stirring was continued for 10 hours under heating conditions of 50 ℃.

The infrared spectrum is adopted to analyze the grease processing byproduct samples before and after polyaspartic acid modification, and the result is shown in figure 2. Referring to fig. 2, curve b represents the raw grease processing byproduct, curve c represents the grease processing byproduct after microwave treatment in step 2, and curve a represents the modified grease processing byproduct in step 3.

From fig. 2, it can be seen that modification of polyaspartic acid can promote hydrogen bond structures to be reformed in biomass molecules after hydrogen bond breaking, so that the hydroxyl absorption peak is shifted to a low wave number.

Example 3A preparation method of a microbial carbon source for modifying a grease processing byproduct comprises the following steps:

step 1: and (3) pretreating 40 ml of the oil processing by-product, adjusting the pH value of the solution to 9 by using 1M sodium hydroxide solution, and stirring at room temperature for 3 hours to promote the residual lipid substances in the oil processing by-product raw material to react to generate the fatty acid sodium soap.

Step 2: and (3) separating and removing impurity substances by a standing precipitation method, standing the grease processing byproduct solution subjected to alkali pretreatment in the step (1) for 12 hours, and pouring supernatant liquid as a processed product.

And step 3: 10 ml of the separated solution water is taken and added with 1 ml of deionized water to adjust the intermolecular hydrogen bonding action, the mixture is stirred at the rotating speed of 300 r/min for 1 hour at room temperature, then 50 microliters of polyacrylic acid (M ═ 2000) is added and the stirring is continued for 10 hours, and the final solution is collected to be used as the carbon source for the microbial denitrification.

Example 4A preparation method of a microbial carbon source of a modified starch wastewater hydrolyzed acidification product comprises the following steps:

step 1: pretreating starch wastewater by 40 ml of hydrolysis acidification product, adjusting the pH value of the solution to 9 by using 1M sodium hydroxide solution, and stirring at room temperature for 3 hours to promote the reaction of residual lipid substances in the raw materials to generate fatty acid sodium soap.

Step 2: and (3) separating the solution obtained in the step (1) by adopting a high-speed rotating centrifuge, treating for 15 minutes at the rotating speed of 5000 r/min, and removing the lower-layer precipitate to obtain a product obtained by treatment.

And step 3: 10 ml of the separated solution was treated under 300W sonication for 20 minutes, 50 μ l polyacrylic acid (M ═ 2000) was added and stirred at 300 rpm for 10 hours at room temperature, and the final solution was collected as a source of carbon for microbial denitrification.

Example 5A preparation method of a modified carbon source of a starch wastewater hydrolysis acidification product comprises the following steps:

step 1: taking 40 ml of starch wastewater hydrolyzed and acidified products, carrying out centrifugal treatment for 10 minutes at the speed of 3000 r/min, and pouring supernatant liquid to be used as a pretreated product.

Step 2: 10 ml of the pretreatment solution from which the insoluble matter was separated was treated under 300W of ultrasonic waves for 20 minutes to adjust the intermolecular hydrogen bonding of the biomass.

And step 3: to the above treatment solution, 50 μ l of polyacrylic acid (M ═ 2000) was added, and stirring was continued for 10 hours under heating conditions of 50 ℃.

Example 6A preparation method of a microbial carbon source for modifying beer saccharification wastewater comprises the following steps:

step 1: pretreating 40 ml of beer saccharification wastewater, adjusting the pH value of the solution to 9 by using 1M sodium hydroxide solution, and stirring at room temperature for 3 hours to promote the reaction of residual lipid substances in the beer saccharification wastewater raw material to generate fatty acid sodium soap.

Step 2: and (3) separating the solution obtained in the step (1) by adopting a high-speed rotating centrifuge, treating for 15 minutes at the rotating speed of 5000 r/min, and removing the lower-layer precipitate to obtain a product obtained by treatment.

And step 3: 10 ml of the separated solution obtained in step 2 was treated by microwave treatment for 2 minutes every 2 minutes under microwave conditions, and was sequentially repeated 10 times, 50. mu.l of polyacrylic acid (M ═ 2000) was added thereto and stirred at room temperature for 10 hours, and the final solution was collected as a carbon source for microbial denitrification.

Example 7A microbial carbon source of a modified starch wastewater hydrolyzed acidification product comprises the following steps:

step 1: pretreating starch wastewater by 40 ml of hydrolysis acidification product, adjusting the pH value of the solution to 9 by using 1M sodium hydroxide solution, and stirring at room temperature for 3 hours to promote the reaction of residual lipid substances in the raw materials to generate fatty acid sodium soap.

Step 2: and (3) separating the solution obtained in the step (1) by adopting a high-speed rotating centrifuge, treating for 15 minutes at the rotating speed of 5000 r/min, and removing the lower-layer precipitate to obtain a product obtained by treatment.

And step 3: 10 ml of the separated solution obtained in step 2 was pre-stirred in a water bath of 60 ℃ at a speed of 300 rpm for 2 hours, 50. mu.l of polyethylene glycol (M600) was added thereto and stirred at room temperature for 10 hours, and the final solution was collected as a carbon source for microbial denitrification.

Example 8A preparation method of a microbial carbon source containing a chemical phosphorus removal agent comprises the following steps:

step 1: pretreating starch wastewater by 40 ml of hydrolysis acidification product, adjusting the pH value of the solution to 9 by using 1M sodium hydroxide solution, and stirring at room temperature for 3 hours to promote the reaction of residual lipid substances in the raw materials to generate fatty acid sodium soap.

Step 2: and (3) separating the solution obtained in the step (1) by adopting a high-speed rotating centrifuge, treating for 15 minutes at the rotating speed of 5000 r/min, and removing the lower-layer precipitate to obtain a product obtained by treatment.

And step 3: 10 ml of the separated solution obtained in step 2 was pre-stirred in a water bath of 60 ℃ at a speed of 300 rpm for 2 hours, 50. mu.l of polyethylene glycol (M600) was added thereto and stirred at room temperature for 10 hours, and the final solution was collected as a carbon source for microbial denitrification.

And 4, step 4: and adding 0.3mmol of ferric chloride of a chemical phosphorus removal agent into the modified carbon source, and stirring for 2 hours at room temperature to obtain the modified organic carbon source mixed with the chemical phosphorus removal agent.

Example 9Preparation method of microbial carbon source containing chemical phosphorus removal agent

The difference from example 8 is that the chemical phosphorus removal agent added is aluminum chloride.

Example 10Preparation method of microbial carbon source containing chemical phosphorus removal agent

The same as in example 1, except that 0.3mmol of zirconium nitrate was added to the microbial denitrification carbon source obtained in step 3.

Example 11Preparation method of microbial carbon source containing chemical phosphorus removal agent

The same as example 2, except that 0.5mmol of lanthanum nitrate was added to the microbial denitrification carbon source obtained in step 3.

Example 12Preparation method of microbial carbon source containing chemical phosphorus removal agent

The same as example 8, except that 0.2mmol of aluminum chloride and 0.1mmol of lanthanum nitrate were added as chemical phosphorus removal agents.

Example 13Preparation method of microbial carbon source containing chemical phosphorus removal agent

The same as example 8, except that the chemical phosphorus removal agents were added in an amount of 0.15mmol of ferric chloride and 0.15mmol of zirconium nitrate.

Application example 1Carbon source strength by using biomassThe biological denitrification denitrogenation method comprises the following steps:

performing denitrification simulation experiment in an anaerobic bottle with the volume of 500mL, maintaining anoxic condition by adopting an SBR operation mode, controlling hydraulic retention for 6h, decanting 200mL of water after reaction is finished each time, supplementing fresh wastewater, adding the modified grease processing by-product prepared in the example 3, the grease processing by-product which is not treated in the example 3 and sodium acetate in a control group in each experiment respectively to enable the initial COD in the experimental reactor of each batch to be 90mg/L, adding sodium nitrate to enable the initial concentration of nitrate nitrogen to be 30mg/L, configuring sludge concentration to be 5000mg/L in each group of experiments, adjusting potassium dihydrogen phosphate to keep total phosphorus to be 4.5mg/L, maintaining water temperature to be 35 ℃, and performing denitrification treatment under anaerobic condition by applying proper stirring.

The solution after the denitrification reaction collected every 6 hours is collected, filtered by a 0.45-micron microfiltration membrane, and then the concentration change of nitrate and nitrite along with the reaction time is measured by ion chromatography, and the actual performance of the carbon source obtained by different modification methods is evaluated, and the result is shown in figure 3.

From fig. 3, it can be seen that the performance of removing nitrate by microbial denitrification varies, the performance of removing nitrate by biomass organic substances before modification fluctuates greatly, and the performance of removing nitrate by carbon sources after modification is better. And, the effect is stable when the experiment sampling is carried out every 6 h. The effect of the carbon source is equivalent to or superior to that of the sodium acetate carbon source commonly used in the prior art, namely, the invention effectively realizes the utilization of the waste biomass product as the carbon source.

Application example 2A method for enhancing biological denitrification nitrogen removal by utilizing a biomass carbon source comprises the following steps:

performing denitrification simulation experiment in an anaerobic bottle with the volume of 500mL, maintaining anoxic condition by adopting an SBR operation mode, controlling hydraulic retention for 6h, decanting 200mL of water after reaction is finished each time, supplementing fresh wastewater, respectively adding the modified grease processing by-product prepared in example 4, the grease processing by-product which is not treated in example 4 and sodium acetate in a control group in each experiment, enabling initial COD (chemical oxygen demand) in each batch of experimental reactors to be 150mg/L, adding sodium nitrate to enable the initial concentration of nitrate nitrogen to be 60mg/L, configuring sludge concentration to be 5000mg/L in each group of experiments, keeping total phosphorus to be 4.5mg/L by adjusting potassium dihydrogen phosphate, maintaining water temperature to be 35 ℃, and performing denitrification treatment under anaerobic condition by applying proper stirring.

The solution after the denitrification reaction collected every 6 hours is collected, filtered by a 0.45-micron microfiltration membrane, and then the concentration change of nitrate and nitrite along with the reaction time is measured by ion chromatography, and the actual performance of the carbon source obtained by different modification methods is evaluated, and the result is shown in figure 4.

From fig. 4, it can be seen that the change in nitrite concentration during the nitrate removal process by microbial denitrification indicates that the modified carbon source can effectively remove nitrate while avoiding the accumulation of nitrite. And, the effect is stable when the experiment sampling is carried out every 6 h. The carbon source has the same effect as or better than the sodium acetate carbon source commonly used in the prior art, namely the application effectively realizes the utilization of waste biomass products as the carbon source.

Application example 3A method for enhancing biological denitrification nitrogen and phosphorus removal by utilizing a biomass carbon source containing a chemical phosphorus removal agent comprises the following steps:

performing denitrification simulation experiment in an anaerobic bottle with the volume of 500mL, maintaining anoxic condition by adopting an SBR operation mode, controlling hydraulic power to stay for 6h, decanting 200mL water after each reaction, supplementing fresh wastewater, adding a hydrolyzed acidification product of the modified starch wastewater containing the ferric chloride chemical phosphorus removal agent prepared in the example 8, a hydrolyzed acidification product of the starch wastewater which is mixed with the ferric chloride chemical phosphorus removal agent and is not treated, and (3) controlling sodium acetate, wherein the initial COD in each batch of experimental reactor is 150mg/L, adding sodium nitrate to ensure that the initial concentration of nitrate nitrogen is 30mg/L, adding monopotassium phosphate to ensure that the initial concentration of inorganic phosphorus is 4mg/L, adding methamidophos to ensure that the initial concentration of organic phosphorus is 0.5mg/L, configuring sludge concentration of 5000mg/L in each group of experiments, maintaining the water temperature at 35 ℃, and performing denitrification and chemical phosphorus removal treatment under anaerobic conditions by applying proper stirring.

Collecting the solution after the denitrification reaction collected every 6 hours, filtering the solution by a 0.45 micron microfiltration membrane, measuring the concentration change of nitrite and phosphorus along with the reaction time by ion chromatography, and evaluating the actual performance of the carbon source obtained by different modification methods, wherein the result is shown in 5.

Referring to fig. 5, in which fig. 5a is a graph showing the change of nitrite concentration during the nitrate removal process by microbial denitrification. FIG. 5b is a diagram showing the change of the total phosphorus concentration during the simultaneous phosphorus removal process by microbial denitrification.

From fig. 5a and fig. 5b, it can be seen that the modified carbon source can effectively remove nitrate while avoiding accumulation of nitrite, and simultaneously keep the total phosphorus concentration below 0.25mg/L, and the denitrification and dephosphorization effects are equivalent to those of the sodium acetate carbon source commonly used in the prior art, i.e. the application effectively realizes the utilization of waste biomass products as the carbon source.

The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.