Composite carbon source material and preparation method and application thereof

Abstract

The present invention provides a composite carbon source material and a preparation method and application thereof, the composite carbon source material comprising a conductive carrier, a first carbon source material and a second carbon source material, the first carbon source material being loaded on at least one surface of the conductive carrier, the first carbon source material comprising an organic acid salt having a relative molecular mass of 60-1000; the second carbon source material being loaded on at least one surface of the conductive carrier, the second carbon source material comprising a core and a pH response layer coated on the surface of the core, wherein the core comprises ecological matrix particles containing carbon, and the pH response layer decomposes to release the core when the pH is greater than or equal to 8.5. The composite carbon source material provided by the embodiment of the present invention can help improve the efficiency of denitrification.

Description

Technical Field

[0001] The present invention relates to the technical field of sewage treatment, and in particular to a composite carbon source material and a preparation method and application thereof. Background Art

[0002] Denitrification generally refers to an eco-chemical process that uses bacteria to reduce nitrates in water to gaseous nitrogen. It is usually used to treat domestic sewage or industrial sewage. Due to the low carbon-nitrogen ratio in sewage, the electron donors required for the eco-chemical process of denitrification are insufficient, so additional carbon sources need to be added as electron donors. However, in the related art, the carbon source added to the denitrification process has limited effect on improving the denitrification efficiency. There is an urgent need to develop a composite carbon source that helps improve the denitrification efficiency. Summary of the invention

[0003] The invention provides a composite carbon source material and a preparation method and application thereof. The composite carbon source material can help improve denitrification efficiency.

[0004] The first aspect of the present invention provides a composite carbon source material, comprising:

[0005] Conductive carrier;

[0006] A first carbon source material is loaded on at least one surface of the conductive carrier, wherein the first carbon source material comprises an organic acid salt with a relative molecular mass of 60-1000;

[0007] A second carbon source material is loaded on at least one surface of the conductive carrier, wherein the second carbon source material includes a core and a pH response layer coated on the surface of the core, wherein the core includes ecological matrix particles containing carbon, and the pH response layer decomposes to release the core when the pH is greater than or equal to 8.5.

[0008] According to any of the aforementioned embodiments of the present invention, the conductive support comprises a conductive carbon material.

[0009] According to any one of the aforementioned embodiments of the present invention, the mass ratio of the first carbon source material to the second carbon source material is 1:(2-5).

[0010] According to any one of the aforementioned embodiments of the present invention, the organic acid salt comprises an organic acid metal salt.

[0011] According to any of the aforementioned embodiments of the present invention, the organic acid in the organic acid metal salt includes at least one of formic acid, acetic acid and propionic acid, and the metal in the organic acid metal salt includes at least one of potassium, magnesium and iron.

[0012] According to any of the aforementioned embodiments of the present invention, the average particle size of the core is 2 mm-50 mm;

[0013] And / or, the pH response layer has a thickness of 5 μm-10 μm.

[0014] According to any of the aforementioned embodiments of the present invention, the material of the ecological matrix particles includes at least one of crop straw and shells.

[0015] According to any of the aforementioned embodiments of the present invention, the pH response layer includes at least one of ester organic matter and amide organic matter.

[0016] The second aspect of the present invention provides a method for preparing the composite carbon source material according to the first aspect of the present invention, comprising:

[0017] The first carbon source material, the second carbon source material and the binder are mixed and coated on at least one surface of the conductive carrier to obtain the composite carbon source material.

[0018] The third aspect of the present invention provides an application of the composite carbon source material as described in the first aspect of the present invention in sewage treatment.

[0019] The embodiment of the present invention provides a composite carbon source material, a preparation method and an application thereof, wherein the composite carbon source material comprises a conductive carrier, a first carbon source material and a second carbon source material, wherein the conductive carrier can conduct electrons, thereby helping to increase the rate of denitrification and denitrification, thereby improving the denitrification efficiency; the first carbon source material is loaded on at least one surface of the conductive carrier, the first carbon source material comprises an organic acid salt with a relative molecular mass of 60-1000, and the first carbon source material can release carbon relatively quickly to promote the rapid progress of denitrification and denitrification; the second carbon source material is loaded on at least one surface of the conductive carrier, the second carbon source material comprises a core and a pH response layer coated on the surface of the core, wherein the core comprises an ecological matrix particle containing carbon, the pH response layer decomposes to release the core when the pH is greater than or equal to 8.5, and the pH response layer in the second carbon source material can help reduce the probability of the pH value in the denitrification and denitrification process exceeding the appropriate pH range for the action of its bacteria, so as to further promote the rapid progress of denitrification and denitrification, and the decomposition of the pH response layer can release the core of the ecological matrix particle containing carbon, which can further provide a carbon source. Therefore, the composite carbon source material provided by the embodiment of the present invention can help improve the denitrification efficiency.

[0020] The above description is only an overview of the technical solution of this specification. In order to more clearly understand the technical means of this specification, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of this specification more obvious and easy to understand, the specific implementation methods of this specification are listed below. DETAILED DESCRIPTION

[0021] The following detailed description specifically discloses the embodiments of the conductive composite material and the preparation method thereof and the products containing the conductive composite material of the present invention. However, there may be cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of well-known matters and repeated descriptions of actually the same structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the following description is provided for those skilled in the art to fully understand the present invention and is not intended to limit the subject matter described in the claims.

[0022] "Scope" disclosed in the present invention is defined in the form of lower limit and upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a particular range. The scope defined in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a particular parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3,4 and 5 are listed, the following scope can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present invention, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this article, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is an integer, for example

[0023] 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0024] If not otherwise specified, all embodiments and optional embodiments of the present invention may be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of the present invention.

[0025] If not otherwise specified, all technical features and optional technical features of the present invention may be combined with each other to form new technical solutions, and such technical solutions should be deemed to be included in the disclosure of the present invention.

[0026] If not otherwise specified, all steps of the present invention may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0027] If there is no special explanation, the "include" and "comprising" mentioned in the present invention represent open-ended or closed-ended expressions. For example, the "include" and "comprising" may represent that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0028] If not specifically stated, in the present invention, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0029] Unless otherwise specified, the terms used in the present invention have the commonly understood meanings that are generally understood by those skilled in the art.

[0030] Unless otherwise specified, the values ​​of the parameters mentioned in the present invention can be measured by various test methods commonly used in the art, for example, they can be measured according to the test methods given in the embodiments of the present invention.

[0031] An embodiment of the present invention provides a composite carbon source material, including: a conductive carrier, a first carbon source material and a second carbon source material, wherein the first carbon source material is loaded on at least one surface of the conductive carrier, and the first carbon source material includes an organic acid salt with a relative molecular mass of 60-1000; the second carbon source material is loaded on at least one surface of the conductive carrier, and the second carbon source material includes a core and a pH response layer coated on the surface of the core, wherein the core includes ecological matrix particles containing carbon, and the pH response layer decomposes to release the core when the pH is greater than or equal to 8.5.

[0032] The composite carbon source material includes a conductive carrier, a first carbon source material and a second carbon source material, wherein the conductive carrier can conduct electrons, thereby helping to increase the rate of denitrification and denitrification, thereby improving the denitrification efficiency; the first carbon source material is loaded on at least one surface of the conductive carrier, the first carbon source material includes an organic acid salt with a relative molecular mass of 60-1000, and the first carbon source material can release carbon relatively quickly to promote the rapid progress of denitrification and denitrification; the second carbon source material is loaded on at least one surface of the conductive carrier, the second carbon source material includes a core and a pH response layer coated on the surface of the core, wherein the core includes ecological matrix particles containing carbon, the pH response layer decomposes to release the core when the pH is greater than or equal to 8.5, and the pH response layer in the second carbon source material can help reduce the probability of the pH value in the denitrification and denitrification process exceeding the appropriate pH range for bacterial action, so as to further promote the rapid progress of denitrification and denitrification, and the decomposition of the pH response layer can release the core of the ecological matrix particles containing carbon, so as to further provide a carbon source. Therefore, the composite carbon source material provided in an embodiment of the present invention can help improve the denitrification efficiency.

[0033] In an embodiment of the present invention, the conductive carrier may have a higher specific surface area, which can not only increase the loading rate of the carbon source material, but also provide a larger reaction area, thereby facilitating denitrification.

[0034] In some embodiments of the present invention, the specific surface area of ​​the conductive support is 500 m 2 / g-3000m 2 / g.

[0035] In some embodiments of the present invention, the conductive carrier includes a conductive carbon material, and the conductive carbon material may be graphite, activated carbon modified with a conductive metal, or the like.

[0036] In an embodiment of the present invention, the mass ratio of the first carbon source material to the second carbon source material is within an appropriate range, which can provide sufficient carbon source for denitrification and denitrification, while also contributing to the rational distribution of the carbon source and further reducing the probability of the pH value in the denitrification process exceeding the appropriate pH range for bacterial action, thereby further improving the denitrification efficiency and reducing the preparation cost of the composite carbon source.

[0037] In some embodiments of the present invention, the mass ratio of the first carbon source material to the second carbon source material is 1:(2-5). The mass ratio of the first carbon source material to the second carbon source material within the above-mentioned suitable range can provide sufficient carbon source for denitrification and denitrification, and can also reduce the increase of pH during the denitrification and denitrification process, thereby helping to provide a better reaction environment for bacteria, thereby further improving the denitrification efficiency.

[0038] Illustratively, the mass ratio of the first carbon source material to the second carbon source material may be 1:2, 1:3, 1:4, or 1:5.

[0039] In addition, the first carbon source material includes suitable materials that can increase the carbon release rate, thereby accelerating the utilization of carbon by bacteria, thereby improving the denitrification efficiency.

[0040] In some embodiments of the present invention, the organic acid salt includes an organic acid metal salt, which can not only quickly release carbon in the water body, but also the released metal can serve as a trace element for bacterial growth, thereby facilitating the rapid reproduction of bacteria to improve denitrification efficiency.

[0041] In some embodiments of the present invention, the relative molecular mass of the organic acid metal salt is 65-500.

[0042] In other embodiments of the present invention, the organic acid in the organic acid metal salt includes at least one of formic acid, acetic acid and propionic acid, and the metal in the organic acid metal salt includes at least one of potassium, magnesium and iron.

[0043] In an embodiment of the present invention, the structure of the second carbon source material can control the release rate of the carbon source and can also reduce the probability of the pH value in the denitrification process exceeding the appropriate pH range for bacterial action.

[0044] In some embodiments of the present invention, the average particle size of the core is 2 mm-50 mm; and the thickness of the pH responsive layer is 5 μm-10 μm.

[0045] In some embodiments of the present invention, the material of the ecological matrix particles includes at least one of crop straw and shell. The crop straw and shell are easy to obtain, which can reduce the preparation cost of the composite carbon source.

[0046] Illustratively, the crop straw may include corn straw, rice straw, wheat straw, soybean straw, and the like.

[0047] In some embodiments of the present invention, the pH responsive layer includes at least one of an ester organic substance and an amide organic substance.

[0048] For example, the ester organic substance may be 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and the amide organic substance may be polyacrylamide.

[0049] The second aspect of the present invention provides a method for preparing the composite carbon source material according to the first aspect of the present invention, comprising:

[0050] The first carbon source material, the second carbon source material and the binder are mixed and coated on at least one surface of the conductive carrier to obtain the composite carbon source material.

[0051] The third aspect of the present invention provides an application of the composite carbon source material as described in the first aspect of the present invention in sewage treatment.

[0052] The following embodiments describe the disclosure of the present invention in more detail, and these embodiments are only for illustrative purposes, because it is obvious to those skilled in the art that various modifications and variations are made within the scope of the disclosure of the present invention. Unless otherwise stated, all parts, percentages and ratios reported in the following embodiments are based on mass, and all reagents used in the embodiments are commercially available or synthesized according to conventional methods, and can be used directly without further processing, and the instruments used in the embodiments are commercially available.

[0053] Example 1

[0054] This embodiment provides a composite carbon source material, including:

[0055] 100 g of sodium formate, 200 g of the second carbon source material and 50 g of polyvinylidene fluoride binder (USA Solvay PVDF So lef 60512) were dispersed in 500 mL of N-methylpyrrolidone solvent to form a first slurry, and then the first slurry was applied to a surface area of ​​500 m 2 / g of activated carbon material is dried at 40°C to obtain a composite carbon source material, wherein the second carbon source material is a corn cob material coated with polyacrylamide (French Aisen AN926SHU), and the second carbon source material is formed by dispersing 50g of polyacrylamide in 200mL of water to form a second slurry, immersing 180g of corn cob material in the second slurry, and taking it out to be dried. The thickness of the polyacrylamide coating layer is 5μm, and the particle size of the corn stalk particles is about 2mm.

[0056] Example 2

[0057] A preparation method similar to that of Example 1 was adopted, except that the mass of the second carbon source material was 300 g.

[0058] Example 3

[0059] A preparation method similar to that of Example 1 was adopted, except that the mass of the second carbon source material was 400 g.

[0060] Example 4

[0061] A preparation method similar to that of Example 1 is adopted, except that the first carbon source material is sodium acetate.

[0062] Example 5

[0063] A preparation method similar to that of Example 1 was adopted, except that the coating material in the second carbon source material was 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.

[0064] Example 6

[0065] A preparation method similar to that of Example 1 was adopted, except that the thickness of the polyacrylamide coating layer was 8 μm.

[0066] Example 7

[0067] A preparation method similar to that of Example 1 was adopted, except that the thickness of the polyacrylamide coating layer was 10 μm.

[0068] Comparative Example 1

[0069] A preparation method similar to that of Example 1 was used, except that the second carbon source material had no pH response layer.

[0070] Comparative Example 2

[0071] A preparation method similar to that of Example 1 is adopted, except that: no conductive carrier is included.

[0072] Test Section

[0073] The composite carbon source materials obtained in Examples 1 to 7 and Comparative Examples 1 to 2 were added to the simulated sewage treatment plant A. 2 In the treatment system of O, the dosage of the composite carbon source material is 20 g / L. The water quality of the inlet water without adding the carbon source, the outlet water without adding the composite carbon source material, and the outlet water with the composite carbon source materials of the embodiment and the comparative example is shown in Table 1 below.

[0074] Table 1: Influent and effluent conditions of different treatments

[0075]

[0076]

[0077] Finally, it should be noted that the above experimental examples are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned experimental examples, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned experimental examples, or replace some or all of the technical features therein with equivalents. These modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the experimental examples of the present invention.

Claims

1. A composite carbon source material, It is characterized in that include: Conductive carrier; A first carbon source material is loaded on at least one surface of the conductive carrier, wherein the first carbon source material comprises an organic acid salt with a relative molecular mass of 60-1000; A second carbon source material is loaded on at least one surface of the conductive carrier, wherein the second carbon source material includes a core and a pH response layer coated on the surface of the core, wherein the core includes ecological matrix particles containing carbon, and the pH response layer decomposes to release the core when the pH is greater than or equal to 8.

5.

2. The composite carbon source material according to claim 1, It is characterized in that The conductive support includes a conductive carbon material.

3. The composite carbon source material according to claim 1, It is characterized in that The mass ratio of the first carbon source material to the second carbon source material is 1:(2-5).

4. The composite carbon source material according to claim 1, It is characterized in that The organic acid salt includes an organic acid metal salt.

5. The composite carbon source material according to claim 4, It is characterized in that The organic acid in the organic acid metal salt includes at least one of formic acid, acetic acid and propionic acid, and the metal in the organic acid metal salt includes at least one of potassium, magnesium and iron.

6. The composite carbon source material according to claim 1, It is characterized in that The average particle size of the core is 2mm-50mm; And / or, the pH response layer has a thickness of 5 μm-10 μm.

7. The composite carbon source material according to claim 1, It is characterized in that The material of the ecological matrix particles includes at least one of crop straw and shells.

8. The composite carbon source material according to claim 1, It is characterized in that The pH response layer includes at least one of ester organic matter and amide organic matter.

9. A method for preparing a composite carbon source material according to any one of claims 1 to 8, It is characterized in that include: The first carbon source material, the second carbon source material and the binder are mixed and coated on at least one surface of the conductive carrier to obtain the composite carbon source material.

10. Use of the composite carbon source material according to any one of claims 1 to 8 in sewage treatment.

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