Preparation method and application of composite photocatalytic filler

Abstract

The present application discloses a preparation method and application of a composite photocatalytic filler, the preparation method comprising: adding a metal solute or an oxide solute to an organic solvent and stirring to obtain a solution to be treated; subjecting the solution to be treated to a hydrothermal treatment to obtain a composite catalyst; subjecting a mixture of the composite catalyst and an oxide solid having a plurality of spherical micropores to a secondary hydrothermal treatment to obtain a catalytic filler precursor; and subjecting the catalytic filler precursor to a calcination treatment to obtain a composite photocatalytic filler. The application is to use the composite photocatalytic filler to remove organic pollutants from biochemical effluent. The present application is beneficial in that it provides a preparation method and application of a composite photocatalytic filler capable of enhancing ozone treatment of biochemical effluent.

Description

Technical Field

[0001] The present application relates to the field of photocatalytic technology, and in particular to a preparation method and application of a composite photocatalytic filler. Background Art

[0002] Among the current water treatment processes, biochemical treatment is the most common. However, for the treatment of some highly difficult wastewater, there are still a lot of difficult-to-degrade organic matter in the biochemical effluent. In order to meet the demand for drainage standards, efficient treatment of biochemical effluent is of great significance.

[0003] Ozone oxidation, as an advanced oxidation technology, has been gradually applied to the deep treatment of wastewater. In recent years, photocatalytic technology has gradually become well-known due to its green, environmentally friendly and efficient characteristics.

[0004] In the related art, when ozone is directly used for oxidation, the problem of low removal rate is encountered.

[0005] Currently, no effective solution has been proposed for the problems in the related technologies. Summary of the invention

[0006] The content of this application is used to introduce concepts in a brief form, which will be described in detail in the detailed implementation section below. The content of this application is not intended to identify the key features or essential features of the technical solution claimed for protection, nor is it intended to limit the scope of the technical solution claimed for protection.

[0007] Some embodiments of the present application propose a preparation method and application of a composite photocatalytic filler to solve the technical problems mentioned in the above background technology section.

[0008] As the first aspect of the present application, some embodiments of the present application provide a method for preparing a composite photocatalytic filler, comprising the following steps: adding a metal solute or an oxide solute to an organic solvent and stirring to obtain a solution to be treated; subjecting the solution to be treated to a hydrothermal treatment to obtain a composite catalyst; subjecting a mixture of the composite catalyst and an oxide solid having a plurality of spherical micropores to a secondary hydrothermal treatment to obtain a catalytic filler precursor; and subjecting the catalytic filler precursor to a calcination treatment to obtain a composite photocatalytic filler; wherein the metal solute comprises one or more metal elements of Fe, Cu, MO, and Cr; the oxide solute comprises one or more of TiO2, Bi2O3, or CoO; the organic solvent comprises an ethanol solution; and the oxide solid comprises Al2O3.

[0009] Furthermore, the metal solute includes metal elements of Fe, Cu, MO, and Cr.

[0010] Further, the oxide solute contains TiO2, Bi2O3 or CoO.

[0011] Furthermore, the metal solute contains equal masses of metal elements of Fe, Cu, Mo, and Cr.

[0012] Further, the oxide solute contains equal masses of TiO2, Bi2O3 or CoO.

[0013] Furthermore, the mass ratio of any metal element in the metal solute to any oxide in the oxide solute ranges from 0.08 to 1.2.

[0014] Furthermore, the mass ratio of any metal element in the metal solute to any oxide in the oxide solute is 0.1.

[0015] Furthermore, the treatment temperature of the hydrothermal treatment is in the range of 200 degrees Celsius to 500 degrees Celsius, and the treatment time is in the range of 4 hours to 12 hours.

[0016] Furthermore, the treatment temperature of the secondary hydrothermal treatment ranges from 200 degrees Celsius to 400 degrees Celsius, and the treatment time ranges from 2 hours to 4 hours.

[0017] Furthermore, the calcination temperature of the calcination treatment ranges from 300 degrees Celsius to 800 degrees Celsius, and the calcination time ranges from 3 hours to 8 hours.

[0018] Furthermore, the particle size of the oxide solid ranges from 1 mm to 10 mm.

[0019] Furthermore, the particle size of the composite photocatalytic filler ranges from 1 mm to 10 mm.

[0020] As a second aspect of the present application, some embodiments of the present application provide an application of a composite photocatalytic filler prepared by the aforementioned preparation method, wherein the composite photocatalytic filler is used to remove organic pollutants from biochemical effluent.

[0021] The beneficial effect of the present application is that it provides a preparation method and application of a composite photocatalytic filler capable of enhancing ozone treatment of biochemical effluent.

[0022] More specifically, some embodiments of the present application may produce the following specific beneficial effects:

[0023] (1) The present application uses hydrothermal and calcination methods to tightly combine metal oxides, metal elements and spherical microporous Al2O3.

[0024] (2) The present application discloses a method for preparing a multi-metal composite photocatalytic filler for enhancing ozone treatment of biochemical effluent. The method utilizes the dual effects of metal oxides and metal elements to generate sufficient photogenerated electrons, thereby promoting the rapid conversion of ozone into hydroxyl radicals, laying a solid foundation for improving the quality of biochemical effluent.

[0025] (3) The present application makes use of multi-metal photocatalytic fillers to fully intervene in the ozone oxidation process, converting as much ozone as possible into hydroxyl radicals required for the reaction. On the basis of maintaining the same ozone dosage, the removal effect of difficult-to-degrade pollutants in the biochemical effluent is significantly and effectively improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The drawings constituting a part of this application are used to provide a further understanding of this application, so that other features, purposes and advantages of this application become more obvious. The illustrative embodiment drawings and their descriptions of this application are used to explain this application and do not constitute an improper limitation on this application.

[0027] In addition, throughout the drawings, the same or similar reference numerals represent the same or similar elements. It should be understood that the drawings are schematic and that the components and elements are not necessarily drawn to scale.

[0028] In the attached picture:

[0029] Figure 1 It is a schematic diagram of the main steps of a method for preparing a composite photocatalytic filler according to an embodiment of the present application. DETAILED DESCRIPTION

[0030] Embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. Although certain embodiments of the present disclosure are shown in the accompanying drawings, it should be understood that the present disclosure can be implemented in various forms and should not be construed as being limited to the embodiments set forth herein. On the contrary, these embodiments are provided to provide a more thorough and complete understanding of the present disclosure. It should be understood that the drawings and embodiments of the present disclosure are only for exemplary purposes and are not intended to limit the scope of protection of the present disclosure.

[0031] It should also be noted that, for ease of description, only the parts related to the invention are shown in the drawings. In the absence of conflict, the embodiments and features in the embodiments of the present disclosure can be combined with each other.

[0032] It should be noted that the concepts such as "first" and "second" mentioned in the present disclosure are only used to distinguish different devices, modules or units, and are not used to limit the order or interdependence of the functions performed by these devices, modules or units.

[0033] It should be noted that the modifications of "one" and "plurality" mentioned in the present disclosure are illustrative rather than restrictive, and those skilled in the art should understand that unless otherwise clearly indicated in the context, it should be understood as "one or more".

[0034] The names of the messages or information exchanged between multiple devices in the embodiments of the present disclosure are only used for illustrative purposes and are not used to limit the scope of these messages or information.

[0035] The present disclosure will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0036] Reference Figure 1 As shown, the preparation method of the composite photocatalytic filler of the present application mainly includes the following steps:

[0037] S100: adding a metal solute or an oxide solute into an organic solvent and stirring the organic solvent to obtain a solution to be treated;

[0038] S200: performing a hydrothermal treatment on the solution to be treated to obtain a composite catalyst;

[0039] S300: performing a secondary hydrothermal treatment on a mixture of the composite catalyst and the oxide solid having a plurality of spherical micropores to obtain a catalytic filler precursor;

[0040] S400: calcining the catalytic filler precursor to obtain a composite photocatalytic filler.

[0041] Among them, the metal solute includes one or more metal elements of Fe, Cu, Mo, and Cr; the oxide solute includes one or more of TiO2, Bi2O3, or CoO; the organic solvent includes an ethanol solution; and the oxide solid includes Al2O3.

[0042] As a specific embodiment, the metal solute includes a single metal substance of Fe, Cu, Mo, or Cr.

[0043] More specifically, the oxide solute comprises TiO2, Bi2O3 or CoO.

[0044] More specifically, the metal solute contains equal masses of metal elements of Fe, Cu, Mo, and Cr.

[0045] More specifically, the oxide solute contains equal masses of TiO2, Bi2O3 or CoO.

[0046] More specifically, the mass ratio of any metal element in the metal solute to any oxide in the oxide solute ranges from 0.08 to 1.2.

[0047] More specifically, the mass ratio of any metal element in the metal solute to any oxide in the oxide solute is 0.1.

[0048] More specifically, the treatment temperature of the hydrothermal treatment is in the range of 200 degrees Celsius to 500 degrees Celsius, and the treatment time is in the range of 4 hours to 12 hours.

[0049] More specifically, the treatment temperature of the secondary hydrothermal treatment ranges from 200 degrees Celsius to 400 degrees Celsius, and the treatment time ranges from 2 hours to 4 hours.

[0050] More specifically, the calcination temperature of the calcination treatment ranges from 300 degrees Celsius to 800 degrees Celsius, and the calcination time ranges from 3 hours to 8 hours.

[0051] More specifically, the particle size of the oxide solid is in the range of 1 mm to 10 mm.

[0052] More specifically, the particle size of the composite photocatalytic filler ranges from 1 mm to 10 mm.

[0053] As a more specific scheme based on the above main steps, the preparation method of the present application may specifically include:

[0054] S10, dissolving one or more metal elements such as Fe, Cu, Mo, Cr, and one of TiO2, Bi2O3 or CoO in ethanol respectively and stirring;

[0055] S20, transferring the sample obtained in step S10 to a high temperature and high pressure reactor and maintaining it at 200 to 500° C. for 4 to 12 hours;

[0056] S30, placing the metal composite catalyst obtained in step S20 and the spherical microporous Al2O3 in a high temperature and high pressure reactor at 200 to 400° C. for 2 to 4 hours;

[0057] S40, placing the photocatalytic filler precursor in step S30 in a muffle furnace for calcination, maintaining the temperature at 300 to 800° C. for 3 to 8 hours, and finally obtaining a photocatalytic filler for enhancing ozone treatment of biochemical effluent.

[0058] The photocatalytic filler described in this application is placed in biochemical effluent, and then ozone is introduced into the water. After illumination, the removal effect of the photocatalytic filler on the difficult-to-degrade organic pollutants in the biochemical effluent is measured. The biochemical effluent is selected from aerobic effluents of a certain pharmaceutical wastewater, coking wastewater and chemical wastewater. The specific steps are as follows: an appropriate amount of filler is placed in biochemical effluent with a COD concentration of 300 to 800 mg / L, and a certain concentration of ozone is introduced into the water. After illumination at 25°C for 60 to 200 minutes, the removal effect of organic pollutants in the biochemical effluent is measured.

[0059] The scheme and effects of the present application are further introduced below in conjunction with embodiments.

[0060] Example 1

[0061] The present embodiment provides a method for preparing a multi-metal composite photocatalytic filler for enhancing ozone treatment of biochemical effluent, and the specific steps are as follows:

[0062] Iron powder and TiO2 are placed in ethanol and stirred thoroughly until they are uniform, wherein 1 g of iron powder and 10 g of TiO2 are taken respectively; the above samples are placed at 300°C for 4 hours using a hydrothermal method; the obtained metal composite catalyst and spherical microporous Al2O3 (particle size 2 mm) are hydrothermally treated again (200°C, 2 hours); finally, the above materials are collected and washed several times with deionized water and alcohol, and then calcined (400°C, 4 hours) to finally obtain a composite filler with a particle size of about 2 mm.

[0063] Then, 100 g of the composite filler was placed in the biochemical effluent, and ozone was then introduced into the water. After irradiation at 25° C., the removal effect of the organic pollutants was measured. The irradiation condition in this embodiment was simulated sunlight.

[0064] The treatment effect of the composite filler on the biochemical effluent in this embodiment is shown in Table 1:

[0065] Table 1 Biochemical effluent treatment effect of Example 1

[0066]

[0067] Example 2

[0068] The basic content of this embodiment is the same as that of Embodiment 1, except that: in this embodiment, the iron powder is replaced with copper powder.

[0069] The treatment effect of the composite filler on the biochemical effluent in this embodiment is shown in Table 2:

[0070] Table 2 Biochemical effluent treatment effect of Example 2

[0071]

[0072] Example 3

[0073] The basic content of this embodiment is the same as that of Embodiment 1, except that in this embodiment, the iron powder is replaced with molybdenum powder.

[0074] The treatment effect of the composite filler on the biochemical effluent in this embodiment is shown in Table 3:

[0075] Table 3 Biochemical effluent treatment effect of Example 3

[0076]

[0077] Example 4

[0078] The basic content of this embodiment is the same as that of Embodiment 1, except that in this embodiment, the iron powder is replaced with chromium powder.

[0079] The treatment effect of the composite filler on the biochemical effluent in this embodiment is shown in Table 4:

[0080] Table 4 Biochemical effluent treatment effect of Example 4

[0081]

[0082] Example 5

[0083] The present embodiment provides a method for preparing a multi-metal composite photocatalytic filler for enhancing ozone treatment of biochemical effluent, and the specific steps are as follows:

[0084] Molybdenum powder and Bi2O3 are placed in ethanol and stirred thoroughly until they are uniform, wherein 1 g of molybdenum powder and 10 g of Bi2O3 are taken respectively; the above samples are placed at 400°C for 6 hours using a hydrothermal method; the obtained metal composite catalyst and spherical microporous Al2O3 (particle size 8 mm) are hydrothermally treated again (300°C, 4 hours); finally, the above materials are collected and washed several times with deionized water and alcohol, and then calcined (400°C, 4 hours) to finally obtain a composite filler with a particle size of about 8 mm.

[0085] Then, 100 g of the composite filler was placed in the biochemical effluent, and ozone was then introduced into the water. After irradiation at 25° C., the removal effect of the organic pollutants was measured. The irradiation condition in this embodiment was simulated sunlight.

[0086] The treatment effect of the composite filler on the biochemical effluent in this embodiment is shown in Table 5:

[0087] Table 5 Biochemical effluent treatment effect of Example 5

[0088]

[0089] Example 6

[0090] The basic content of this embodiment is the same as that of Embodiment 5, except that: in this embodiment, Bi2O3 is replaced by CoO.

[0091] The treatment effect of the composite filler on the biochemical effluent in this embodiment is shown in Table 6:

[0092] Table 6 Biochemical effluent treatment effect of Example 6

[0093]

[0094] Example 7

[0095] The present embodiment provides a method for preparing a multi-metal composite photocatalytic filler for enhancing ozone treatment of biochemical effluent, and the specific steps are as follows:

[0096] Iron powder, molybdenum powder and Bi2O3 are placed in ethanol and stirred thoroughly until they are uniform, wherein 0.5, 0.5 and 10 g of iron powder, molybdenum powder and Bi2O3 are taken respectively; the above samples are placed at 400°C for 8 hours using a hydrothermal method; the obtained metal composite catalyst and spherical microporous Al2O3 (particle size 5 mm) are hydrothermally treated again (400°C, 4 hours); finally, the above materials are collected and washed several times with deionized water and alcohol, and then calcined (500°C, 4 hours) to finally obtain a composite filler with a particle size of about 5 mm.

[0097] Then, 100 g of the composite filler was placed in the biochemical effluent, and ozone was then introduced into the water. After irradiation at 25° C., the removal effect of the organic pollutants was measured. The irradiation condition in this embodiment was simulated sunlight.

[0098] The treatment effect of the composite filler on the biochemical effluent in this embodiment is shown in Table 7:

[0099] Table 7 Biochemical effluent treatment effect of Example 7

[0100]

[0101] Example 8

[0102] The basic content of this embodiment is the same as that of Embodiment 7, except that: in this embodiment, the iron powder is replaced with copper powder.

[0103] The treatment effect of the composite filler on the biochemical effluent in this embodiment is shown in Table 8:

[0104] Table 8 Biochemical effluent treatment effect of Example 8

[0105]

[0106] Comparative Example 1

[0107] In this study, a blank experiment was conducted by adding only ozone to the biochemical effluent, and the removal effect of ozone on the refractory organic matter in the water was measured after illumination. See Table 9 for details:

[0108] Table 9 Biochemical effluent treatment effect of comparative example 1

[0109]

[0110] Comparative Example 2

[0111] The basic content of this comparative example is the same as that of comparative example 1, except that the self-degradation effect of the refractory organic matter in the biochemical effluent is explored without adding ozone.

[0112] The self-degradation effect of the biochemical effluent in this comparative example is shown in Table 10:

[0113] Table 10 Biochemical effluent self-degradation effect of comparative example 2

[0114]

[0115] It can be seen from the above examples and comparative examples that the composite photocatalytic filler containing metal elements used in the present application can effectively improve the removal rate of organic waste in wastewater.

[0116] The above is a schematic description of the present application and its implementation methods, which is not restrictive, and the data used is only one of the implementation methods of the present application, and the actual data combination is not limited thereto. Therefore, if a person skilled in the art is inspired by it, without departing from the purpose of the present application, the implementation methods and embodiments similar to the technical solution without creative design should all fall within the scope of protection of the present application.

[0117] Those skilled in the art should understand that the scope of the invention involved in the embodiments of the present disclosure is not limited to the technical solutions formed by a specific combination of the above technical features, but should also cover other technical solutions formed by any combination of the above technical features or their equivalent features without departing from the above inventive concept. For example, the above features are replaced with (but not limited to) technical features with similar functions disclosed in the embodiments of the present disclosure.

Claims

1. A method for preparing a composite photocatalytic filler, characterized in that: The steps include: adding a metal solute and an oxide solute into an organic solvent and stirring the mixture to obtain a solution to be treated; Performing a hydrothermal treatment on the solution to be treated to obtain a composite catalyst; Performing a secondary hydrothermal treatment on a mixture of the composite catalyst and an oxide solid having a plurality of spherical micropores to obtain a catalytic filler precursor; Calcining the catalytic filler precursor to obtain a composite photocatalytic filler; Wherein, the metal solute is one or more of the metal elements of Fe, Cu, Mo or Cr; the oxide solute is one or more of TiO2, Bi2O3 or CoO; the organic solvent is an ethanol solution; the oxide solid is Al2O3; The treatment temperature of the secondary hydrothermal treatment ranges from 200 degrees Celsius to 400 degrees Celsius, and the treatment time ranges from 2 hours to 4 hours; The mass ratio of any metal element in the metal solute to any oxide in the oxide solute is in the range of 0.08 to 1.2; The obtained composite photocatalytic filler generates sufficient photogenerated electrons by virtue of the dual effects of metal oxides and metal elements, thereby promoting the rapid conversion of ozone into hydroxyl radicals.

2. The method for preparing the composite photocatalytic filler according to claim 1, characterized in that: The metal solute is a metal single substance of Fe, Cu, Mo or Cr.

3. The method for preparing the composite photocatalytic filler according to claim 1, characterized in that: The oxide solute is TiO2, Bi2O3 or CoO.

4. The method for preparing the composite photocatalytic filler according to claim 1, characterized in that: The mass ratio of any metal element in the metal solute to any oxide in the oxide solute is 0.

1.

5. The method for preparing the composite photocatalytic filler according to claim 1, characterized in that: The treatment temperature of the primary hydrothermal treatment ranges from 200 degrees Celsius to 500 degrees Celsius, and the treatment time ranges from 4 hours to 12 hours.

6. The method for preparing the composite photocatalytic filler according to claim 1, characterized in that: The calcination temperature of the calcination treatment ranges from 300 degrees Celsius to 800 degrees Celsius, and the calcination time ranges from 3 hours to 8 hours.

7. The method for preparing the composite photocatalytic filler according to claim 1, characterized in that: The particle size of the oxide solid ranges from 1 mm to 10 mm.

8. The method for preparing the composite photocatalytic filler according to claim 1, characterized in that: The particle size of the composite photocatalytic filler ranges from 1 mm to 10 mm.

9. An application of the composite photocatalytic filler prepared by the preparation method according to any one of claims 1 to 8, wherein the composite photocatalytic filler is used to remove organic pollutants from biochemical effluent.

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