A method for recycling of sulfocarbamide waste liquid

Abstract

The present application relates to a kind of resource utilization methods of sulfolane waste liquid, the method comprises: the sulfolane waste liquid is mixed with photocatalyst and then carries out dark reaction and photocatalytic reaction in turn;Wherein, the photocatalyst is multi-stage hole silicon oxide / C3N4 Compound photocatalyst.The resource utilization method of sulfolane waste liquid provided by the present application is suitable for the resource utilization of sulfolane waste liquid containing small molecule organic pollutants and inorganic salt.By introducing large specific surface area multi-stage hole silicon oxide / C3N4 Photocatalyst, under the condition of normal temperature and pressure, without additional organic reagent, the adsorption enrichment and conversion of sulfolane waste liquid are realized, wherein sulfolane is converted into cyclobutane and sulfuric acid, and cyclobutane is directly overflowed in the form of gas, avoiding the time and energy consumption cost caused by separation;Small molecule organic pollutants in liquid are degraded under the action of photocatalysis, and only sulfuric acid generated in solution and a small amount of inorganic salt originally in waste liquid exist, and resource utilization can be realized by separating salt.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of waste liquid treatment, in particular to a resource utilization method of sulfolane waste liquid. BACKGROUND

[0002] The sulfolane waste liquid is a hazardous waste produced by an aromatic hydrocarbon device. At present, the distillation method is mainly used in industry for treating the sulfolane waste liquid. However, due to the high water content in the waste liquid, the energy consumption of the evaporation method is very large, and the high temperature can easily cause the ring-opening reaction of sulfolane and other side reactions. When the biochemical method is used to treat the sulfolane waste liquid, the sulfolane is degraded into carbon dioxide and sulfur dioxide, etc., which cannot be resourcefully utilized. Therefore, the harmless and resourceful technology of sulfolane waste liquid with high efficiency and energy saving is in urgent need in the market.

[0003] In recent years, the resource utilization technology of sulfolane waste liquid has attracted the attention of the technical personnel in the field. For example, Luoyang Petrochemical uses delayed coking technology to send sulfolane to the top of the coke tower for recycling, which opens up a "green channel" for the treatment of sulfolane waste agent. However, due to the high sulfur content in sulfolane, harmful waste gas such as hydrogen sulfide or sulfur dioxide is generated in the process, which increases the burden of waste gas treatment and the energy consumption is high.

[0004] Patent 200610134285.3 discloses a recovery method of sulfolane containing inorganic salt. The inorganic salt is precipitated by using a filter aid, and then the filter aid is evaporated by vacuum distillation, so as to remove the inorganic salt in the sulfolane. The method has high efficiency and simple operation, but the filter aid is methylbenzene which is an easy-to-poison reagent, and the method can only remove specific inorganic salt and cannot remove other small-molecule organic pollutants in the waste liquid.

[0005] Patent 201810857047.8 recovers sulfolane in waste liquid by using extraction method. The concentration of sulfolane in the treated waste liquid is less than 50 mg / L. However, the extraction agent used in the method is a mixture of one or more than two of halogenated hydrocarbons, aromatic hydrocarbons and ester compounds, and the amount used is large. Moreover, the small-molecule organic pollutants in the waste liquid cannot be removed. Therefore, although the concentration of sulfolane in the treated waste liquid is less than 50 mg / L, the COD is still higher than 100 mg / L, which cannot meet the discharge standard. Due to the existence of small-molecule organic matter and inorganic salt, the recycling of the treated waste water is also limited. SUMMARY

[0006] The purpose of the present application is to provide a resource utilization method of sulfolane waste liquid, which solves the problems of high energy consumption, high toxicity and difficulty in treating small-molecule organic pollutants in the waste liquid in the traditional method.

[0007] In order to achieve the above object, the application provides a resource utilization method of sulfallutamide waste liquid, which comprises the following steps: mixing the sulfallutamide waste liquid with a photocatalyst, and then sequentially performing dark reaction and photocatalytic reaction; wherein the photocatalyst is a multi-level pore silicon oxide / C3N4 composite photocatalyst.

[0008] Optionally, the multi-level pore silicon oxide / C3N4 composite photocatalyst comprises multi-level pore silicon oxide and C3N4 quantum dots doped in the multi-level pore silicon oxide; the weight percentage of the multi-level pore silicon oxide is 10% to 40% and the weight percentage of the C3N4 quantum dots is 60% to 90% based on the total weight of the multi-level pore silicon oxide / C3N4 composite photocatalyst; and the specific surface area of the multi-level pore silicon oxide / C3N4 composite photocatalyst is 600 to 1000 m 2 / g.

[0009] Optionally, the addition amount of the multi-level pore silicon oxide / C3N4 composite photocatalyst is 0.1 to 5 g / L based on the volume of the sulfallutamide waste liquid.

[0010] Optionally, the COD in the sulfallutamide waste liquid is 20 to 3000 mg / L, the concentration of sulfallutamide is 10 to 1000 mg / L, and the concentration of sulfate is 0 to 100 mg / L.

[0011] Optionally, the conditions of the dark reaction comprise: light intensity of 0 to 0.1 mW / cm 2 , time of 10 to 60 min, preferably 20 to 40 min; and the conditions of the photocatalytic reaction comprise: light intensity of 20 to 80 mW / cm 2 , light time of 4 to 8 h; and the light source is a 300 W xenon lamp pre-installed with a 400 to 800 nm filter.

[0012] Optionally, the preparation method of the multi-level pore silicon oxide / C3N4 composite photocatalyst comprises:

[0013] S1, mixing coal gasification fly ash with an alkali solution and performing microwave heating reaction; performing first solid-liquid separation on the reaction product to obtain first solid product desilicated ash and first solution;

[0014] S2, mixing the first solution, a surfactant and acetic acid and performing hydrothermal crystallization to obtain second solution;

[0015] S3, performing second solid-liquid separation on the second solution to obtain second solid product; mixing and stirring the second solid product, deionized water and melamine to obtain third solution;

[0016] S4, performing third solid-liquid separation on the third solution to obtain third solid product; and calcining the third solid product.

[0017] Optionally, the mass ratio of the coal gasification fly ash to the alkali in the alkali solution is 1:(0.5-1.0); the alkali in the alkali solution is one or more of NaOH, KOH or LiOH, preferably NaOH; the concentration of the alkali solution is 10-30%; the concentration of silicon in the first solution is 3000-8000 mg / L, preferably 4000-7000 mg / L.

[0018] Optionally, the mass ratio of the second solid product to melamine is 1:(2-14), preferably 1:(5-10).

[0019] Optionally, the molar ratio of the surfactant to the first solution in terms of silicon is (0.06-0.4):1, preferably (0.1-0.2):1; the surfactant is selected from at least one of cetyl trimethyl ammonium bromide, cetyl triethyl ammonium bromide and bromo cetyl pyridine, preferably cetyl trimethyl ammonium bromide.

[0020] Optionally, the microwave heating reaction condition includes: the microwave heating temperature is 100-150 DEG C, and the time is 10-50 min; the hydrothermal crystallization condition includes: the temperature is 50-150 DEG C, preferably 100-120 DEG C; the time is 8-48 h, preferably 16-32 h; the calcination condition includes: the temperature is 400-700 DEG C, preferably 500-600 DEG C; the time is 1-8 h, preferably 2-5 h.

[0021] By the above technical solution, the resource utilization method of the sulfolane waste liquid provided by the application is suitable for the resource utilization of the sulfolane waste liquid containing small-molecule organic pollutants and inorganic salts. By introducing the large specific surface area multi-stage pore silicon oxide / C3N4 photocatalyst, the adsorption enrichment and conversion of the sulfolane waste liquid are realized under the conditions of normal temperature and pressure and without additional organic reagents, wherein the sulfolane is converted into cyclobutane and sulfuric acid, and the cyclobutane directly overflows in the form of gas, avoiding the time and energy consumption cost caused by separation; the small-molecule organic pollutants in the liquid are degraded under the photocatalytic action, and only the sulfuric acid generated in the reaction and a small amount of inorganic salts originally in the waste liquid exist in the solution, and the resource utilization can be realized by separating the salts.

[0022] Other features and advantages of the present application will be described in detail in the following specific embodiments. BRIEF DESCRIPTION OF DRAWINGS

[0023] The accompanying drawings are included to provide a further understanding of the application, and constitute a part of the specification, and are used together with the following specific embodiments to explain the application, but do not constitute a limitation on the application. In the drawings:

[0024] Figure 1It is an electron microscope graph of the multi-level hole silicon oxide / C3N4 composite photocatalyst in the embodiment 1 of the present application. DETAILED DESCRIPTION

[0025] The specific embodiments of the present application are described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely intended to illustrate and explain the present application, and are not intended to limit the present application.

[0026] The present application provides a resource utilization method of sulfolane waste liquid, which comprises: mixing the sulfolane waste liquid with a photocatalyst, and then sequentially performing dark reaction and photocatalytic reaction; wherein the photocatalyst is a multi-level hole silicon oxide / C3N4 composite photocatalyst.

[0027] In the present application, the resource utilization method of sulfolane waste liquid is a method for converting sulfolane in sulfolane waste liquid and completely degrading small molecule organic pollutants under visible light irradiation by using multi-level hole silicon oxide / C3N4 as a catalyst. The method provided by the present application is green, energy-saving, simple and efficient. Under the conditions of normal temperature and pressure and without additional organic reagents, sulfolane in sulfolane waste liquid can be converted into cyclobutane and sulfuric acid by adsorption and enrichment. Cyclobutane directly overflows in the form of gas, avoiding the time and energy cost caused by separation. Small molecule organic pollutants in the liquid are degraded under the action of photocatalysis. Only sulfuric acid generated by the reaction and a small amount of inorganic salts originally present in the waste liquid exist in the solution, which is conducive to the reuse of the waste liquid.

[0028] According to the present application, the multi-level hole silicon oxide / C3N4 composite photocatalyst comprises multi-level hole silicon oxide and C3N4 quantum dots doped in the multi-level hole silicon oxide. In the present application, C3N4 exists in the form of quantum dots, multi-level hole silicon oxide has a dual-level hole structure including large holes and small holes, and multi-level hole silicon oxide has a large specific surface area, thus having good adsorption performance. The multi-level hole silicon oxide / C3N4 composite photocatalyst formed by the C3N4 quantum dots is beneficial to light absorption and has good degradation effect on sulfolane waste liquid.

[0029] According to the present application, the weight percentage of the multi-level hole silicon oxide is 10% to 40% and the weight percentage of the C3N4 quantum dots is 60% to 90% based on the total weight of the multi-level hole silicon oxide / C3N4 composite photocatalyst; and the specific surface area of the multi-level hole silicon oxide / C3N4 composite photocatalyst is 600 to 1000 m 2 / g. The above embodiments can improve the photocatalytic performance of the multi-level hole silicon oxide / C3N4 composite photocatalyst, and better convert sulfolane in sulfolane waste liquid and degrade small molecule organic pollutants.

[0030] According to the application, the adding amount of the multi-level pore silicon oxide / C3N4 composite photocatalyst is 0.1-5 g / L, optionally based on the volume of the sulfolane waste liquid.

[0031] According to the application, the COD in the sulfolane waste liquid is 20-3000 mg / L, the concentration of sulfolane is 10-1000 mg / L, and the concentration of sulfate is 0-100 mg / L.

[0032] According to the application, the conditions of the dark reaction include that the light intensity is 0-0.1 mW / cm 2 , the time is 10-60 min, preferably 20-40 min; the conditions of the photocatalytic reaction include that the light intensity is 20-80 mW / cm 2 , the light time is 4-8 h; and the light source is a 300 W xenon lamp pre-installed with a 400-800 nm filter.

[0033] According to the application, the preparation method of the multi-level pore silicon oxide / C3N4 composite photocatalyst comprises:

[0034] S1, mixing coal gasification fly ash and an alkali solution, and performing microwave heating reaction; performing first solid-liquid separation on the reaction product to obtain first solid product desilicated ash and a first solution;

[0035] S2, mixing the first solution, a surfactant and acetic acid, and performing hydrothermal crystallization to obtain a second solution;

[0036] S3, performing second solid-liquid separation on the second solution to obtain a second solid product; mixing and stirring the second solid product, deionized water and melamine to obtain a third solution;

[0037] S4, performing third solid-liquid separation on the third solution to obtain a third solid product; and calcining the third solid product.

[0038] The multi-level pore silicon oxide / C3N4 composite photocatalyst prepared by the preparation method has better light absorption and good degradation effect on the sulfolane waste liquid.

[0039] According to the application, the mass ratio of the coal gasification fly ash to the alkali in the alkali solution is 1:(0.5-1.0); the alkali in the alkali solution is one or more of NaOH, KOH or LiOH, preferably NaOH; and the concentration of the alkali solution is 10-30%. In the application, the coal gasification fly ash is used as a silicon source to prepare a multi-level pore silicon oxide precursor, and meanwhile, the coal gasification fly ash can be recycled.

[0040] According to the application, optionally, the concentration of silicon element in the first solution is 3000-8000 mg / L, preferably 4000-7000 mg / L.

[0041] According to the application, optionally, the mass ratio of the second solid product to melamine is 1:(2-14), preferably 1:(5-10). In the application, melamine is loaded in the hierarchical porous silicon oxide, and a hierarchical porous silicon oxide / C3N4 composite photocatalyst is obtained through subsequent calcination.

[0042] According to the application, optionally, the molar ratio of the surfactant to the first solution in terms of silicon element is (0.06-0.4):1, preferably (0.1-0.2):1; the surfactant is selected from at least one of cetyltrimethylammonium bromide, cetyltriethylammonium bromide and bromohexadecylpyridine, preferably cetyltrimethylammonium bromide.

[0043] According to the application, optionally, the microwave heating reaction condition includes that the microwave heating temperature is 100-150℃, and the time is 10-50 min; the hydrothermal crystallization condition includes that the temperature is 50-150℃, preferably 100-120℃; the time is 8-48 h, preferably 16-32 h; the calcination condition includes that the temperature is 400-700℃, preferably 500-600℃; the time is 1-8 h, preferably 2-5 h.

[0044] The application is further illustrated by the following examples, but the application is not limited in any way by the examples.

[0045] The coal gasification fly ash used in the examples is from a chemical plant in Anqing, referred to as Anqing ash. The main chemical composition (by weight) includes SiO2(49.4%), Al2O3(22.8%), CaO(10.3%), Fe2O3(8.21%), TiO2(1.26%), Na2O(1.22%), MgO(0.83%), and the rest is residual carbon.

[0046] Example 1

[0047] A resource utilization method of a sulfolane waste liquid, the steps of which are as follows:

[0048] (1) Preparation of photocatalyst: 3 g of coal gasification fly ash was weighed into a polytetrafluoroethylene digestion tube, 6 mL of 20% NaOH solution was added, the same raw materials were added into four tubes, and then the tubes were placed in a microwave digestion instrument for reaction at 130°C under microwave auxiliary heating for 30 min. Then, solid-liquid separation was performed to obtain desilicated ash and a first solution. The first solution was combined, and the concentration of silicon in the first solution was adjusted to 5 g / L. 100 mL of the first solution was accurately measured, 1.04 g of CTAB was added, and after stirring uniformly, acetic acid was added to adjust the pH to 11.0. Then, the solution was transferred into a 200 mL hydrothermal kettle, and hydrothermal treatment was performed at 110°C for 24 h to obtain a second solution. The second solution was centrifuged to obtain a second solid product. The second solid product was washed to neutral, 1.0 g of the second solid product was mixed with 30 mL of deionized water and 8.6 g of melamine to obtain a third solution. The third solution was centrifuged to obtain a multi-level porous silica powder loaded with melamine. The powder was placed in a crucible, and after covering the crucible with a lid, the crucible was calcined in a muffle furnace at 550°C for 4 h to obtain a multi-level porous silica / C3N4 composite photocatalyst. The electron microscope image of the photocatalyst is shown in FIG. 1, and it can be seen that C3N4 quantum dots are loaded on the multi-level porous silica. The weight percentage of multi-level porous silica in the multi-level porous silica / C3N4 composite photocatalyst is 15.2%, and the weight percentage of C3N4 is 84.8%. The specific surface area of the multi-level porous silica / C3N4 composite photocatalyst is 755 m2 / g. Figure 1 2

[0049] (2) A 300 W xenon lamp (light intensity: 50 mW / cm 2 ) with a pre-installed 400-800 nm filter was used to perform visible light catalytic treatment on a sulfolane waste liquid to which 2 g / L of the multi-level porous silica / C3N4 composite photocatalyst was added. Before the light source was turned on, dark adsorption of the composite photocatalyst and the sulfolane waste liquid was performed (light intensity: 50 mW / cm 2 ). After adsorption equilibrium was reached, the photocatalytic experiment was started. The dark adsorption time was 30 min. In this embodiment, the COD of the sulfolane waste liquid to be treated was 2573 mg / L, the concentration of sulfolane was 135 mg / L, and the concentration of sulfate was 34 mg / L. After adsorption for 30 min, the COD of the waste liquid was 2061 mg / L, and the concentration of sulfate was 32 mg / L. After 6 h of photocatalytic reaction, the COD of the waste liquid was 0 mg / L, and the concentration of sulfate ions was 140 mg / L.

[0050] It was calculated that the COD removal rate was 99.5%, and the sulfur element in sulfolane was completely converted into sulfate.

[0051] Example 2

[0052] A method for resource utilization of a sulfolane waste liquid comprises the following steps:​​

[0053] (1) Preparation of photocatalyst: 3 g of coal gasification fly ash was weighed into a polytetrafluoroethylene digestion tube, 6 mL of 20% NaOH solution was added, the same raw materials were added into four tubes, and then placed in a microwave digestion instrument under the condition of microwave auxiliary heating at 130°C for 30 min. Then, solid-liquid separation was performed to obtain desilicated ash and a first solution. The first solution was combined, and the concentration of silicon in the first solution was adjusted to 5 g / L. 100 mL of the first solution was accurately measured, 1.04 g of CTAB was added, and after stirring uniformly, acetic acid was added to adjust the pH to 11.0. Then, it was transferred into a 200 mL hydrothermal kettle, and hydrothermal treatment was performed at 110°C for 24 h to obtain a second solution. The second solution was centrifuged to obtain a second solid product. The second solid product was washed to neutral, 1.2 g of the second solid product was mixed with 30 mL of deionized water and 8.6 g of melamine to stir for 30 min to obtain a third solution. The third solution was centrifuged to obtain a multi-level porous silica powder loaded with melamine. The powder was placed in a crucible, and after covering the lid, calcination was performed in a muffle furnace at 550°C for 4 h to obtain a multi-level porous silica / C3N4 composite photocatalyst. The weight percentage of multi-level porous silica in the multi-level porous silica / C3N4 composite photocatalyst was 11.1%, and the weight percentage of C3N4 was 88.9%. The specific surface area of the multi-level porous silica / C3N4 composite photocatalyst was 741 m 2 / g.

[0054] (2) A 300 W xenon lamp (light intensity: 50 mW / cm 2 ) with a pre-installed 400-800 nm filter was used for visible light catalytic treatment of sulfolane waste liquid to which 2 g / L of multi-level porous silica / C3N4 composite photocatalyst was added. Before the light source was turned on, dark adsorption of the composite photocatalyst and the sulfolane waste liquid was performed (light intensity: 50 mW / cm 2 ). After adsorption equilibrium was reached, the photocatalytic experiment was started. The dark adsorption time was 30 min. In this example, the COD of the sulfolane waste liquid to be treated was 400 mg / L, the concentration of sulfolane was 97.5 mg / L, and the concentration of sulfate was 32 mg / L. After 30 min of adsorption, the COD of the waste liquid was 265 mg / L, and the concentration of sulfate was 32 mg / L. After 6 h of photocatalytic reaction, the COD of the waste liquid was 6 mg / L, and the concentration of sulfate ions was 110 mg / L.

[0055] It was calculated that the COD removal rate was 98.5%, and the sulfur element in sulfolane was completely converted into sulfate.

[0056] Comparative Example 1

[0057] The test method of the present comparative example is the same as that of Example 1, except that no photocatalyst is added to the waste liquid, which is directly irradiated under visible light. Specifically, the 300W xenon lamp with a pre-installed 400-800nm filter is used to perform visible light catalytic treatment on the sulfolane waste liquid. The COD concentration of the sulfolane waste liquid used is 2573mg / L, and the sulfate radical concentration is 38.0mg / L. After 30 minutes of adsorption, the COD concentration of the waste liquid is 2573mg / L, and the sulfate radical concentration is 38.0mg / L. After 6 hours of photocatalytic reaction, the COD in the waste liquid is 2548mg / L, and the concentration of sulfate ions is 32mg / L.

[0058] It is calculated that the COD removal rate is 1%, and the sulfur in sulfolane is not converted into sulfate.

[0059] The preferred embodiments of the present application are described in detail above with reference to the accompanying drawings, but the present application is not limited to the specific details in the above-described embodiments. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, and these simple modifications all belong to the protection scope of the present application.

[0060] In addition, it should be noted that each specific technical feature described in the above-described specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present application will not further describe various possible combinations.

[0061] Furthermore, various different embodiments of the present application can also be combined in any manner, as long as they do not deviate from the technical concept of the present application, and they should also be considered as disclosed content of the present application.

Claims

1. A method for resource utilization of sulfocarbamide waste liquid, characterized in that, The method comprises: mixing the ring sulfone waste liquid with a photocatalyst, and then sequentially performing a dark reaction and a photocatalytic reaction; wherein the photocatalyst is a multi-level pore silicon oxide / C3N4 composite photocatalyst; the multi-level pore silicon oxide / C3N4 composite photocatalyst comprises multi-level pore silicon oxide and C3N4 quantum dots doped in the multi-level pore silicon oxide; and the specific surface area of the multi-level pore silicon oxide / C3N4 composite photocatalyst is 600-1000 m 2 / g.

2. The method of claim 1, wherein, The weight percentage of the multi-level pore silicon oxide is 10% to 40% and the weight percentage of the C3N4 quantum dot is 60% to 90% based on the total weight of the multi-level pore silicon oxide / C3N4 composite photocatalyst.

3. The method of claim 1, wherein, The addition amount of the multi-level pore silicon oxide / C3N4 composite photocatalyst is 0.1 to 5 g / L based on the volume of the sulfolane waste liquid.

4. The method of claim 1, wherein, The COD in the sulfolane waste liquid is 20 to 3000 mg / L, the concentration of sulfolane is 10 to 1000 mg / L, and the concentration of sulfate is 0 to 100 mg / L.

5. The method of claim 1, wherein, The conditions of the dark reaction include: light intensity is 0~0.1mW / cm 2 , time is 10~60min; the conditions of the photocatalytic reaction include: light intensity is 20~80mW / cm 2 , light time is 4~8h; light source is 300W xenon lamp with 400~800nm filter.

6. The method of claim 5, wherein, The time in the condition of the dark reaction is 20 to 40 min.

7. The method of claim 1, wherein, The preparation method of the multi-level pore silicon oxide / C3N4 composite photocatalyst comprises: S1, mixing coal gasification fly ash and an alkali solution, and performing microwave heating reaction; performing first solid-liquid separation on the reaction product to obtain a first solid product desilicated ash and a first solution; S2, mixing the first solution, a surfactant and acetic acid, and performing hydrothermal crystallization to obtain a second solution; S3, performing second solid-liquid separation on the second solution to obtain a second solid product; mixing and stirring the second solid product, deionized water and melamine to obtain a third solution; S4, performing third solid-liquid separation on the third solution to obtain a third solid product; and calcining the third solid product.

8. The method of claim 7, wherein, The mass ratio of the coal gasification fly ash to the alkali in the alkali solution is 1: (0.5-1.0); The alkali in the alkali solution is one or more of NaOH, KOH or LiOH; and the concentration of the alkali solution is 10-30%. The concentration of silicon element in the first solution is 3000-8000 mg / L.

9. The method of claim 8, wherein, The alkali in the alkali solution is NaOH; and the concentration of silicon element in the first solution is 4000-7000 mg / L.

10. The method of claim 7, wherein, The mass ratio of the second solid product to melamine is 1: (2-14).

11. The method of claim 10, wherein, The mass ratio of the second solid product to melamine is 1: (5-10).

12. The method of claim 7, wherein, The molar ratio of the surfactant to the first solution calculated based on silicon element is (0.06-0.4): 1; The surfactant is at least one selected from cetyltrimethylammonium bromide, cetyltriethylammonium bromide and bromohexadecylpyridine.

13. The method of claim 12, wherein, The molar ratio of the surfactant to the first solution calculated based on silicon element is (0.1-0.2): 1; The surfactant is cetyltrimethylammonium bromide.

14. The method of claim 7, wherein, The microwave heating reaction condition comprises: microwave heating temperature is 100-150℃, and time is 10-50 min; The hydrothermal crystallization condition comprises: temperature is 50-150℃; and time is 8-48 h; The calcination condition comprises: temperature is 400-700℃; and time is 1-8 h.

15. The method of claim 14, wherein, The hydrothermal crystallization condition comprises: temperature is 100-120℃; and time is 16-32 h; The calcination condition comprises: temperature is 500-600℃; and time is 2-5 h.

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