Bioenhancer based on molybdenum disulfide composite material, preparation method and application thereof

Abstract

The present application provides a bioenhancer based on a molybdenum disulfide composite material, and a preparation method and an application thereof. The main components of the molybdenum disulfide composite material include molybdenum disulfide and graphene, and a ratio of a mass of the molybdenum disulfide composite material to a volume of the activated sludge in the bioenhancer is (1100) g:5000 mL; the molybdenum disulfide crystal phase with the above-mentioned enhancement characteristics includes 1T crystal phase and 2H crystal phase.

Claims

1. A bioenhancer based on a molybdenum disulfide composite material, comprising: the molybdenum disulfide composite material and activated sludge, wherein a ratio of a mass of the molybdenum disulfide composite material to a volume of the activated sludge is (1100) g:5000 mL; and the molybdenum disulfide composite material is prepared by: subjecting a solution containing ammonium molybdate tetrahydrate, thioacetamide, and graphene to hydrothermal treatment; wherein a mass ratio of ammonium molybdate tetrahydrate, thioacetamide, and graphene is 2.5:(1.52):(0.10.5); the hydrothermal treatment is conducted at a temperature of 180400 C. for 1832 hours; the molybdenum disulfide composite material comprises molybdenum disulfide and graphene; and the molybdenum disulfide comprises molybdenum disulfide with a 1T crystal phase and molybdenum disulfide with a 2H crystal phase.

2. An application of the bioenhancer based on the molybdenum disulfide composite material according to claim 1 in nitrogen-containing wastewater, comprising: adding the bioenhancer into a biochemical system, wherein a volume ratio of the bioenhancer to the biochemical system is 1:10 to 1:100.

3. The application according to claim 2, further comprising subsequent maintenance steps: supplementing the bioenhancer to the biochemical system, wherein a ratio of a mass of the molybdenum disulfide composite material in the supplemented bioenhancer to a volume of the biochemical system is 1 g:10000 mL to 1 g:500000 mL; and wherein an interval between each subsequent maintenance step is 1 to 3 days.

4. A method for preparing a bioenhancer based on a molybdenum disulfide composite material, comprising: mixing the molybdenum disulfide composite material with activated sludge; wherein the molybdenum disulfide composite material comprises molybdenum disulfide and graphene, and a ratio of a mass of the molybdenum disulfide composite material to a volume of the activated sludge is (1100) g:5000 mL.

5. The method according to claim 4, wherein a time of mixing the molybdenum disulfide composite material and the activated sludge is 0.5 to 3 days.

6. The method according to claim 4, wherein: an intensity of the mixing is 50100 Nm.sup.3/(m.sup.2.Math.h), and the mixing is continuous.

7. An application of the bioenhancer prepared by the method according to claim 4 in nitrogen-containing wastewater, wherein: adding the bioenhancer into a biochemical system, wherein a volume ratio of the bioenhancer to the biochemical system is 1:10 to 1:100.

8. The application according to claim 7, further comprising subsequent maintenance steps: supplementing the bioenhancer to the biochemical system, wherein a ratio of a mass of the molybdenum disulfide composite material in the supplemented bioenhancer to a volume of the biochemical system is 1 g:10000 mL to 1 g:500000 mL; and wherein an interval between each subsequent maintenance step is 1 to 3 days.

9. An activated sludge strengthening method based on a molybdenum disulfide composite material, comprising: adding the molybdenum disulfide composite material into an anoxic biochemical section of a biochemical system, wherein a ratio of a mass of the molybdenum disulfide composite material to a volume of the biochemical system is 1 g:5000 mL to 1 g:50000 mL; and wherein the molybdenum disulfide composite material is prepared by: subjecting a solution containing ammonium molybdate tetrahydrate, thioacetamide, and graphene to hydrothermal treatment; wherein a mass ratio of ammonium molybdate tetrahydrate, thioacetamide, and graphene is 2.5:(1.52):(0.10.5); the hydrothermal treatment is conducted at a temperature of 180400 C. for 1832 hours; the molybdenum disulfide composite material comprises molybdenum disulfide and graphene; and the molybdenum disulfide comprises molybdenum disulfide with a 1T crystal phase and molybdenum disulfide with a 2H crystal phase.

10. The method according to claim 9, further comprising enhanced maintenance steps, wherein the enhanced maintenance steps comprise: adding the molybdenum disulfide composite material to the biochemical system, wherein a ratio of a mass of the molybdenum disulfide composite material to a volume of the biochemical system is 1 g:10000 mL to 1 g:500000 mL; and wherein an interval between each two enhanced maintenance steps is 1 to 3 days.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) The present application may be more easily understood by reference to the following description in conjunction with examples, all of which constitute a part of the present application. It should be understood that the present application is not limited to the specific products, methods, conditions or parameters described and/or illustrated herein. In an embodiment, the terms used herein are only used for the purpose of describing specific embodiments by way of example and are not intended to be limiting unless otherwise indicated.

(2) It should also be understood that, for the sake of clarity, certain features of the present application may be described herein in the context of separate embodiments, but may also be provided in combination with each other in a single embodiment. That is, unless clearly incompatible or specifically not included, each separate embodiment is considered to be combinable with any other embodiment, and the combination is considered to represent another different embodiment. Conversely, for the sake of simplicity, the various features of the present application described in the context of a single embodiment may also be provided individually or in any sub-combination. Finally, although a particular embodiment may be described as part of a series of steps or part of a more general structure, each step or substructure itself may also be considered to be an independent embodiment.

(3) Unless otherwise indicated, it should be understood that each individual element in a list and each combination of individual elements in the list will be interpreted as a different embodiment. For example, a list of embodiments represented as A, B, or C should be interpreted to include embodiments A, B, C, A or B, A or C, B or C, or A, B, or C.

(4) In the present application, the singular forms of the articles a, an, and the further include the corresponding plural references, and a reference to a specific value includes at least that specific value unless the context clearly indicates otherwise. Thus, for example, a reference to a substance is a reference to at least one of that substance and its equivalents.

(5) Terms including ordinal numbers such as first and second can be used to explain various components or fluids, but these components and fluids are not limited by these terms. Therefore, without departing from the teachings of the present application, these terms are only used to distinguish the component/fluid from another component/fluid.

(6) When items are described by using the conjunction terms . . . and/or . . . , etc., the description should be understood to include any one of the associated listed items and all combinations of one or more thereof.

(7) In general, the use of the term about indicates an approximate value that may vary depending on the desired properties obtained by the disclosed subject matter, and will be interpreted in a context-dependent manner based on function. Therefore, one of those skilled in the art will be able to interpret a certain degree of difference on a case-by-case basis. In some cases, the number of significant figures used when expressing a particular value can be a representative technique for determining the difference allowed by the term about. In other cases, a gradient in a range of values can be used to determine the range of differences allowed by the term about. In an embodiment, all ranges in this disclosure are inclusive and combinable, and reference to a value in a range includes each value within that range.

(8) Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of those skilled in the art to which the application belongs; the terms used herein and/or include any and all combinations of one or more of the associated listed items.

(9) In the following examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if no manufacturer is specified, are all conventional products that can be purchased commercially.

(10) The present application is further described below with reference to specific examples, but the examples do not limit the present application in any form. Unless otherwise specified, the reagents, methods and equipment used in the present application are conventional reagents, methods and equipment in the present technical field. The essential features and remarkable effects of the present application can be reflected in the following embodiments. The described embodiments are part of the embodiments of the present application, but not all of the embodiments. Therefore, they do not limit the present application in any way. Those skilled in the art may make some non-essential improvements and adjustments based on the contents of the present application, which all fall within the protection scope of the present application.

Embodiment 1

(11) In this embodiment, a bioenhancer is provided, which includes a molybdenum disulfide composite material and activated sludge. The ratio of the molybdenum disulfide composite material to the activated sludge in the bioenhancer is 1 g:1000 mL.

(12) Based on this, this embodiment further provides a specific method for preparing the above-mentioned bioenhancer.

(13) S1, preparing molybdenum disulfide composite material: dissolving ammonium molybdate tetrahydrate (2.5 g), thioacetamide (1.5 g) and graphene (0.1 g) in 35 mL of deionized water by sonication and stirring for 15 minutes to obtain solution C; transferring solution C to a polytetrafluoroethylene liner in an autoclave and heating at 200 C. for 24 hours; after cooling to room temperature, washing alternately three times by ultrapure water and ethanol to obtain a molybdenum disulfide composite material.

(14) S2, preparing the bioenhancer: preparing a bioenhancer based on the molybdenum disulfide composite material prepared in step S1: stirring and mixing, at about 25 C. (normal temperature), the molybdenum disulfide composite material and activated sludge (activated sludge from the anoxic biochemical section of the pharmaceutical wastewater biochemical treatment system) at a ratio of 1 g:1000 mL, where the composite material and the activated sludge are first rapidly stirred and mixed at a stirring speed of 150 rpm for 0.5 h, and then slowly stirred at a stirring speed of 80 rpm for 24 h to obtain a bioenhancer labeled MSC-B-1.

Comparative Example 1-1

(15) This comparative example is basically the same as the above-mentioned embodiment 1, except that step S1.

(16) In S1 described in this comparative example, graphene is not added in the process of preparing the molybdenum disulfide composite material, to obtain the molybdenum disulfide composite material.

(17) Finally, the corresponding bioenhancer was prepared based on the molybdenum disulfide composite material obtained in this comparative example, and was labeled D-MSC-B-1.

Embodiment 2

(18) This embodiment is basically the same as the above-mentioned Embodiment 1, except that in step S2: the mixing ratio of the molybdenum disulfide composite material and the activated sludge is 1 g:200 mL, and finally a bioenhancer is obtained, which is labeled MSC-B-2.

Embodiment 3

(19) This embodiment is basically the same as the above-mentioned Embodiment 1, except that in step S2: the mixing ratio of the molybdenum disulfide composite material and the activated sludge is 1 g:50 mL, and finally a bioenhancer is obtained, which is labeled MSC-B-3.

Comparative Example 1-2

(20) This comparative example is basically the same as the above-mentioned Embodiment 1, except that in step S2: the mixing ratio of the molybdenum disulfide composite material and the activated sludge is 1 g:7000 mL, and the bioenhancer is finally obtained, which is labeled D-MSC-B-2.

Comparative Examples 1-3

(21) This comparative example is basically the same as the above-mentioned Embodiment 1, except that in step S2: the mixing ratio of the molybdenum disulfide composite material and the activated sludge is 1 g:10 mL, and finally a bioenhancer is obtained, which is labeled D-MSC-B-3.

Embodiment 4

(22) Based on the above embodiments and comparative examples, the prepared bioenhancer is applied to the denitrification of nitrogen-containing wastewater. The specific process is: adding the bioenhancer to the anoxic biochemical section of the biochemical system, the volume ratio of the bioenhancer to the volume of the biochemical system is 1:80, where the volume of the biochemical system is 1 L, which is used to simulate the biological denitrification of wastewater. The influent total nitrogen (TN) is 56 mg/L, the residence time is 16 hours, the temperature is room temperature (about 22 C.), and the supernatant of the effluent is taken for nitrogen-related indicators testing.

(23) TABLE-US-00001 TABLE 1 Treatment results of nitrogen-containing wastewater with different bioenhancers Bioenhancer MSC-B-1 MSC-B-2 MSC-B-3 D-MSC-B-1 D-MSC-B-2 D-MSC-B-3 Inlet TN (mg/L) 56 56 56 56 56 56 Outlet TN 25 10 7 43 39 6 (mg/L) TN removal rate 55.4% 82.1% 87.5% 23.2% 30.4% 89.3%

(24) According to the data in Table 1, based on the experimental data of bioenhancers MSC-B-1 and D-MSC-B-1, it can be seen that when graphene is not added to the molybdenum disulfide composite material, the TN removal effect is poor due to the lack of graphene for electron transfer. Based on the experimental data of bioenhancers MSC-B-1, MSC-B-2 and MSC-B-3, as the amount of molybdenum disulfide composite material in the bioenhancer increases, the TN removal rate shows a trend of gradual increase. Combined with the data of bioenhancers D-MSC-B-2 and D-MSC-B-3, when the amount of molybdenum disulfide composite material in the bioenhancer is small, molybdenum disulfide produces fewer electrons, resulting in poor denitrification effect. When the amount of molybdenum disulfide composite material in the bioenhancer is large, the denitrification effect is only slightly improved, but the treatment cost is greatly increased.

Comparative Example 4-1

(25) The method is basically the same as Embodiment 4, except that no bioenhancer is added to the biochemical system. The TN removal rate achieved is 12%.

(26) It can be seen that when no bioenhancer is added, the denitrification effect is poor.

Embodiment 5

(27) Subsequent maintenance steps: Based on the application of the bioenhancer MSC-B-1 prepared in Embodiment 4 to the denitrification of nitrogen-containing wastewater, the TN removal rate is detected every 8 hours. After operating for 24 hours, when subsequent maintenance steps are required, the bioenhancer is supplemented to the biochemical system every day. The ratio of the mass of the molybdenum disulfide composite material in the supplemented bioenhancer to the volume of the biochemical system is 1 g:100000 mL, and the denitrification removal rate of the biochemical system can be maintained at 52%61% every day.

Embodiment 6

(28) The method of directly performing activated sludge strengthening using the molybdenum disulfide composite material prepared by step S1 in the above embodiment 1, the specific process is: adding the molybdenum disulfide composite material to the anoxic biochemical section of the biochemical system, the ratio of the mass of the molybdenum disulfide composite material to the volume of the biochemical system is 1 g:16000 mL, where the volume of the biochemical system is 1 L, which is used to simulate the biological denitrification of wastewater. The influent TN is 56 mg/L, the residence time is 16 hours, the temperature is room temperature (about 22 C.), and the supernatant of the effluent is obtained for nitrogen-related indicators testing, the effluent TN is 12 mg/L, and the TN removal rate is 78.6%.

Embodiment 7

(29) Based on the molybdenum disulfide composite activated sludge enhancement method in Embodiment 6, the TN removal rate is detected every 8 hours. After operating for 24 hours, when the enhanced maintenance step is required, the molybdenum disulfide composite material is supplemented to the biochemical system every day. The ratio of the mass of the supplemented molybdenum disulfide composite material to the volume of the biochemical system is 5 g:1000000 mL, and the denitrification removal rate of the biochemical system can be maintained at 71%83% every day.

(30) It should be understood that those skilled in the art will recognize that some variations that can be directly derived or associated from the disclosure of the present application and common knowledge under the motivation from the concept of the present application and its particular examples, those skilled in the art will recognize that. Other methods, or alternatives to well-known techniques commonly used in the related art, and insubstantial modifications of different combinations of features, etc., can be applied as well, and the functions and effects described in the present application can be implemented, and examples will not be explained in detail but is within the scope of the present application.