Application of a copper-based core-shell material in adsorbing and enriching multi-component organic and inorganic sulfur pollutants

Abstract

The present invention discloses an application of a copper-based core-shell material in adsorbing and enriching multi-component organic and inorganic sulfur pollutants, belonging to the technical field of sulfur pollutant treatment. The preparation method comprises the following steps: dissolving nano-CuO, a reducing agent, a templating agent and a surfactant in water, adding a silicon source, and then stirring and calcining to obtain a CuO@Sp·SiO2 adsorbent with nano-CuO as the core and spherical SiO2 as the shell; wherein, the mass ratio of the nano-CuO to the silicon source is (0.05-0.3):1. By the above preparation method, the CuO nano-core is ingeniously wrapped in the SiO2 shell, and after calcination, a core-shell CuO@Sp·SiO2 adsorbent is prepared, breaking through the inherent structure of traditional adsorbents. Due to its unique core-shell structure and electron-metal carrier interaction, the desulfurization efficiency of the adsorbent is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of sulfur pollutant treatment, and particularly relates to the application of a copper-based core-shell material in the adsorption and enrichment of multi-component organic and inorganic sulfur pollutants. Background Art

[0002] Sulfur-containing malodorous pollutants have a low olfactory threshold and strong toxicity. They not only pose a major threat to human health and living quality, but may also cause serious atmospheric environmental pollution such as smog, so they have become key and difficult problems to be solved urgently in the field of environmental protection. The emission of sulfur-containing malodorous pollutants is also quite serious in the pulp and paper industry. Globally, the pulp and paper industry is considered one of the six major polluting industries, second only to the petroleum, cement, leather, textile, and steel industries, and has been continuously discharging a large amount of sulfur-containing pollutants into the natural environment for a long time. In view of this, the industry urgently needs to adopt innovative and efficient environmental protection technologies.

[0003] The emission of sulfur-containing pollutants mainly comes from the processing and use of natural wood, and these activities will release various harmful atmospheric sulfur-containing pollutants. Existing literature reports the main components of sulfides, including thiols and thioethers, such as methanethiol (CH3SH) and dimethyl disulfide (CH3SSCH3).

[0004] The current waste gas treatment technologies in the pulp and paper industry mainly include adsorption method, absorption method, catalytic oxidation method, direct combustion method, and biological treatment method. These treatment technologies often focus on the removal of single pollutants. However, in actual waste gas emissions, there are often multiple sulfur-containing pollutants, and these pollutants may interact with each other, making it difficult for a single technology to achieve an ideal treatment effect. Therefore, when facing complex multi-component sulfur-containing waste gas, the existing technologies are greatly limited in terms of treatment efficiency and applicable range.

[0005] The adsorption method has been widely used in the field of industrial pollution control due to its high separation ability and relatively low operating cost. However, for the treatment of waste gas with a wide variety of sulfur-containing pollutants, the application of adsorption technology is relatively limited, especially in the removal of low-concentration sulfur-containing pollutants. In order to effectively address this challenge, it has become particularly urgent to develop more comprehensive and efficient waste gas treatment technologies, including the development of an integrated purification system that can simultaneously remove multiple sulfur-containing pollutants, and the exploration of new catalysts and adsorption materials to improve treatment efficiency and reduce operating costs. Summary of the Invention

[0006] In view of the above technical problems, the present invention provides an application of a copper-based core-shell material in adsorbing and enriching multi-component organic and inorganic sulfur pollutants. The adsorbent obtained by the preparation method of the present invention has a core-shell structure, wherein the core is macroporous CuO and the shell is mesoporous silica; the introduction of the SiO2 shell layer not only realizes the directional adsorption of sulfur-containing atmosphere, but also effectively prevents the rapid deactivation of the adsorbent caused by sulfur and carbon deposition; and by utilizing the strong interaction between the electron-metal carrier interaction of the adsorbent and the adsorbed species, the desulfurization efficiency of the adsorbent is significantly improved.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] A preparation method of a core-shell CuO@Sp·SiO2 (wherein Sp represents the spherical Sphere formed during the synthesis) adsorbent, comprising the following steps:

[0009] Dissolve nano-CuO, a reducing agent, a templating agent and a surfactant in water, then add a silicon source, and then stir and calcine to obtain a CuO@Sp·SiO2 adsorbent with nano-CuO as the core and spherical SiO2 as the shell;

[0010] Wherein, the mass ratio of the nano-CuO to the silicon source is (0.05-0.3):1.

[0011] Beneficial effects: The adsorption of CuO@Sp·SiO2 mainly combines chemical adsorption and physical adsorption. The core nano-CuO provides active sites, while the SiO2 shell layer enhances its chemical stability and prevents the loss of CuO. Under specific conditions, the SiO2 in the shell layer can control the entry of molecules through the pore structure and improve the selective adsorption ability for certain target substances. When this material is used for adsorption reaction, the catalytic activity of nano-CuO can react more effectively with reactants by increasing the contact area, and at the same time, the protective effect of the SiO2 shell layer can extend the service life of this catalyst.

[0012] Preferably, the reducing agent includes ethanol;

[0013] The templating agent includes cetyltrimethylammonium bromide and / or cetyltrimethylammonium chloride;

[0014] The surfactant is one of triethanolamine or diethanolamine;

[0015] The silicon source includes tetraethyl orthosilicate.

[0016] Beneficial effects: As the core material, nano-CuO has good catalytic performance and adsorption capacity. Its large specific surface area enables it to effectively adsorb target molecules. The reducing agent ethanol can regulate the electrochemical properties and adsorption capacity of the material during the preparation process. The use of the template agent can effectively control the shape and thickness of the SiO2 shell, ensuring the spherical structure of the final product, which helps to improve the fluidity and dispersibility of the material. The surfactant can reduce the surface tension of the system, improve the dispersibility, ensure the uniform combination of nano-CuO and SiO2, avoid aggregation, and increase the effective reaction area.

[0017] Preferably, the time during the stirring process is 16 - 24 h, and the stirring speed is 500 - 600 r / min.

[0018] Preferably, the conditions during the calcination process are as follows:

[0019] Calcine at 500 - 600 °C for 6 - 10 h.

[0020] Beneficial effects: Dissolving each raw material in water and fully stirring aims to ensure the uniform mixing of each component, promoting the uniformity and efficiency of the reaction. The selection of the calcination temperature and time is crucial and should be optimized according to the thermal stability and reaction rate of the material. For example, choosing a moderate temperature (such as 500 - 600 °C) can effectively promote the formation of SiO2 while ensuring the stable existence of nano-CuO. The stirring speed should be adjusted to 500 - 600 r / min. Too fast may cause the generation of bubbles, affecting the uniformity of deposition; too slow may lead to incomplete reactions.

[0021] Technical solution two:

[0022] The core-shell CuO@SiO2 adsorbent prepared by the above preparation method.

[0023] Preferably, the average diameter of the CuO@SiO2 adsorbent core is 51 - 52 nm, and the average diameter of the entire spherical CuO@SiO2 adsorbent is 137 - 138 nm.

[0024] Beneficial effects: When this material is used in the adsorption reaction, the catalytic activity of nano-CuO can react more effectively with the reactants by increasing the contact area, and at the same time, the protective effect of the SiO2 shell can extend the service life of this catalyst.

[0025] Technical solution three:

[0026] Application of the above core-shell CuO@Sp·SiO2 adsorbent in the adsorption and removal of multi-component and / or single-component sulfur-containing pollutants.

[0027] Preferably, the multi-component sulfur-containing pollutants include three-component and two-component;

[0028] Among them, the three-component sulfur-containing pollutant is: CH3SH, CH3SSCH3 and H2S, and the volume ratio of the three is 3:2:7;

[0029] The two-component sulfur-containing pollutant is: CH3SH and CH3SSCH, and the volume ratio of the two is 9:1.

[0030] Preferably, the single-component sulfur-containing pollutant includes any one of CH3SH, CH3SSCH3 and H2S; more preferably H2S.

[0031] Beneficial effects: The CuO@Sp·SiO2 adsorbent can efficiently adsorb multi-component and single-component sulfur-containing pollutants, showing good applicability and broad application potential, and can treat various different types of sulfur sources. CH3SH: It has strong reducibility and is widely present in natural gas and petroleum. Due to its strong odor, it has a significant impact on the environment. The active sites of the adsorbent contribute to its efficient removal. CH3SSCH3: As a disulfide, its structure is complex and can be efficiently removed through appropriate adsorption mechanisms (such as chemisorption). H2S: It is a common and highly toxic sulfide, and the adsorbent of the present invention can be used to achieve efficient removal, reducing environmental and health risks.

[0032] The fourth technical solution of the present invention:

[0033] A method for adsorptive removal of multi-component or single-component sulfur-containing pollutants, comprising the following steps:

[0034] Introduce the sulfur-containing pollutant gas into a reactor containing the above-mentioned core-shell CuO@SiO2 adsorbent, and carry out adsorptive removal at normal temperature and pressure, room temperature conditions.

[0035] Preferably, the ratio of the total sulfur concentration of the sulfur-containing pollutant gas to the dosage of the core-shell CuO@SiO2 adsorbent is: 1000 ppm: 0.2 - 0.3 g.

[0036] Preferably, the flow rate of introducing the sulfur-containing pollutant gas is 30 - 40 mL / min.

[0037] Beneficial effects: Introduce the sulfur-containing pollutant gas into the reactor at a flow rate of 30 - 40 mL / min. This flow rate design optimizes the contact time between the gas and the adsorbent, thereby improving the adsorption efficiency. The reaction is carried out at normal temperature and pressure, and the operating conditions are simple, without the need for expensive equipment and complex temperature control measures, which more meets the requirements of actual production. The total sulfur concentration of the sulfur-containing pollutant gas is 1000 ppm, and the dosage of the core-shell CuO@SiO2 adsorbent is 0.2 - 0.3 g. Such a ratio setting ensures that the adsorbent is used to achieve the best effect, which can not only efficiently remove pollutants but also help save raw material costs.

[0038] Compared with the prior art, the present invention has the following advantages and technical effects:

[0039] (1) The adsorbent of the present invention has a unique core-shell structure. The outer layer of the CuO nano-core is wrapped with a SiO2 shell, and the core-shell CuO@Sp·SiO2 adsorbent is obtained after calcination. The introduction of the mesoporous structure (SiO2 shell) during the synthesis process significantly increases the specific surface area of the material and realizes the pore structure transformation from macropores (CuO core) to mesopores. It also protects the internal active sites, thereby enhancing its sulfur and carbon resistance, achieving the adsorption and removal of multi-component sulfur-containing pollutants, and having good application prospects.

[0040] (2) The present invention cleverly wraps the CuO nano-core in the SiO2 shell and prepares the core-shell CuO@Sp·SiO2 adsorbent after calcination, breaking through the inherent structure of traditional adsorbents. By utilizing the strong interaction between the electron-metal carrier interaction of the adsorbent and the adsorbed species, the desulfurization efficiency of the adsorbent is significantly improved.

[0041] (3) The core-shell CuO@Sp·SiO2 adsorbent prepared by the present invention has the following advantages compared with the existing adsorbents for adsorbing and removing sulfur-containing pollutants:

[0042] 1) Simultaneously removing multi-component sulfur-containing pollutants: The core-shell CuO@Sp·SiO2 adsorbent prepared by the present invention can simultaneously adsorb and remove multi-component sulfur-containing pollutants including three-component, two-component and single-component gases at normal pressure and 25-30 °C. Compared with the single gas component of traditional adsorbents, it is more in line with the actual working conditions and has a wider application range.

[0043] 2) High activity and low energy consumption: Compared with traditional silica and alumina-based adsorbents modified with alkali metals or alkaline earth metals, the core-shell CuO@Sp·SiO2 adsorbent prepared by the present invention can achieve an adsorption and removal efficiency of sulfur-containing pollutants of 100% at normal pressure and 25-30 °C. The required temperature and pressure are much lower than those of alumina-based adsorbents (160 °C, 1.2 MPa, 100% conversion) and silica adsorbents modified with alkali metals or alkaline earth metals (1-5 atm, 20-50 °C, <100%). BRIEF DESCRIPTION OF THE DRAWINGS

[0044] The drawings forming a part of this application are used to provide a further understanding of this application. The schematic embodiments of this application and their descriptions are used to explain this application and do not constitute an improper limitation to this application. In the drawings:

[0045] Figure 1 is the adsorption activity of the adsorbents prepared in Example 1, Comparative Example 1 and Comparative Example 2 under a three-component reaction gas (CH3SH, CH3SSCH3 and H2S);

[0046] Figure 2 The adsorption activities of the adsorbents prepared in Example 1, Comparative Example 1, and Comparative Example 2 under a two-component reaction gas (CH3SH, CH3SSCH3);

[0047] Figure 3 The adsorption activities of the adsorbents prepared in Example 1, Comparative Example 1, and Comparative Example 2 under a single-component reaction gas (H2S);

[0048] Figure 4 The TEM image of the core-shell CuO@Sp·SiO2 adsorbent prepared in Example 1 of the present invention. Detailed implementation manners

[0049] Now, various exemplary implementation manners of the present invention will be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, characteristics, and implementation schemes of the present invention.

[0050] It should be understood that the terms described in the present invention are only for describing particular implementation manners and are not used to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0051] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0052] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific implementation manners of the specification of the present invention, which are obvious to those skilled in the art. Other implementation manners obtained from the specification of the present invention are also obvious to those skilled in the art. The specification and examples of the present invention are only exemplary.

[0053] Regarding the terms "comprising", "including", "having", "containing", etc. used herein, they are all open-ended terms, meaning including but not limited to.

[0054] The present invention discloses a preparation method of a core-shell CuO@Sp·SiO2 adsorbent, comprising the following steps:

[0055] Dissolve CuO nanocores, a reducing agent, a templating agent, and a surfactant in water, then add a silicon source, stir and react, and collect the precipitate (the precipitate is core-shell CuO@Sp·SiO2), and calcine the precipitate to remove the excess templating agent and organic matter to obtain the core-shell CuO@Sp·SiO2 adsorbent.

[0056] In some preferred embodiments, the CuO nanocores are commercially available nano-CuO purchased as the core:

[0057] In some preferred embodiments, the reducing agent includes ethanol;

[0058] The templating agent includes cetyltrimethylammonium bromide;

[0059] The surfactant includes triethanolamine; at the same time, triethanolamine can also be used as a solvent to promote the dissolution of tetraethyl orthosilicate;

[0060] The silicon source includes tetraethyl orthosilicate.

[0061] In some preferred embodiments, the stirring reaction time is 16 - 24 h.

[0062] In some preferred embodiments, the mass ratio of CuO nanocores to the silicon source is (0.05 - 0.3):1.

[0063] In some preferred embodiments, the average diameter of the CuO core of the finally prepared core-shell CuO@Sp·SiO2 is 51 - 52 nm, and the average diameter of the sphere is 137 - 138 nm;

[0064] The thickness of the SiO2 shell in the core-shell CuO@Sp·SiO2 catalyst is about 86 nm (137 - 51 = 86).

[0065] In some preferred embodiments, the preparation method includes the following steps:

[0066] Disperse 112 - 186 mg of nano-CuO cores in a certain amount of a mixed solvent of deionized water and ethanol, and alternately stir and ultrasonically treat until uniform. Then, add 2.9 - 3.2 g of cetyltrimethylammonium bromide (CTAB) and 0.8 - 1.2 mL of triethanolamine. Stir the mixture evenly, and then add 1.6 - 2.5 mL of tetraethyl orthosilicate (TEOS) to the solution. The solution is stirred at room temperature for 16 - 24 hours, the resulting solid is separated by centrifugation, washed with an acetone-ethanol co-solvent, and dried overnight in an oven. Finally, the dried material is placed in a tube furnace and calcined at 500 - 600 °C for 6 - 10 h, and taken out after cooling to room temperature to obtain a CuO@Sp·SiO2 core-shell sphere adsorbent with a theoretical loading of 20 - 30%.

[0067] In addition, the present invention also provides a core-shell CuO@Sp·SiO2 adsorbent prepared by the above preparation method.

[0068] Use of the above core-shell CuO@Sp·SiO2 adsorbent in adsorptive removal of multi-component and / or single-component sulfur-containing pollutants (H2S / CH3SH / CH3SSCH3).

[0069] In some preferred effect examples, use of the above core-shell CuO@Sp·SiO2 adsorbent in adsorptive removal of a three-component sulfur-containing gas (CH3SH, CH3SSCH3 and H2S), a two-component sulfur-containing gas (CH3SH and CH3SSCH3), and a single sulfur-containing gas (H2S).

[0070] A method for adsorptive removal of multi-component sulfur-containing pollutants, comprising the following steps:

[0071] (1) During the experiment, a constant total sulfur content (1000 ppm) was maintained and distributed to three different reaction gases. The first system contains three sulfur-containing gases: CH3SH, CH3SSCH3 and H2S;

[0072] The second system consists of two sulfur-containing gases: CH3SH and CH3SSCH3;

[0073] The third system contains only a single sulfur-containing gas, namely H2S.

[0074] (2) The above three gas systems were respectively introduced into a device equipped with the above core-shell CuO@Sp·SiO2 catalyst, and under normal pressure, the experimental adsorption temperature was 40 °C, and the total gas flow rate was 30-40 mL / min, adsorptive removal of multi-component sulfur-containing pollutants was carried out.

[0075] In the present invention, "room temperature" refers to 20-30 °C unless otherwise specified.

[0076] In the present invention, "parts" refers to parts by mass unless otherwise specified.

[0077] All raw materials used in the present invention are obtained by purchasing on the market. The nano-CuO (purchased from Shanghai Macklin Biochemical Co., Ltd.), cetyltrimethylammonium chloride (purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.), triethanolamine, and tetraethyl orthosilicate used in the following examples are all commercially available products, and the drug purity is analytical pure and does not require further purification.

[0078] The technical solution of the present invention will be further described below through examples.

[0079] Example 1

[0080] A preparation method of a core-shell CuO@Sp·SiO2 adsorbent, comprising the following steps:

[0081] Disperse 120 mg of nano-CuO cores in a mixed solvent of 220 mL of deionized water and ethanol (volume ratio of ethanol to water = 1.75:1), and alternately stir and ultrasonically treat until uniform. Then, add 3 g of cetyltrimethylammonium bromide (CTAB) and 0.9 mL of triethanolamine. Stir the mixture evenly, and then add 1.8 mL of tetraethyl orthosilicate (TEOS) to the solution. The solution is stirred at 500 - 600 r / min at room temperature overnight, and the obtained solid is separated by centrifugation, washed with an acetone-ethanol co-solvent, and dried in an oven overnight. Finally, the dried material is placed in a tubular furnace and calcined at 600 °C for 7 h, and taken out after cooling to room temperature to obtain a CuO@Sp·SiO2 core-shell sphere adsorbent with a theoretical loading of 21%.

[0082] Figure 4 This is the TEM image of the core-shell CuO@Sp·SiO2 adsorbent prepared in Example 1 of the present invention. It can be seen from the figure that the calcined core-shell CuO@Sp·SiO2 adsorbent has an obvious core-shell structure, and the interface between the inner core (black) and the outer shell (gray) can be clearly identified. The existence of this interface proves the formation of the core-shell structure. By precise measurement, the average diameter of the spheres is determined to be 137 - 138 nm, while the average diameter of the inner core is 51 - 52 nm. Thus, it can be known that the shell thickness is about 86 nm, indicating the successful preparation of the adsorbent.

[0083] Comparative Example 1

[0084] A preparation method of a CuO / MCM-41 adsorbent (this material is synthesized by the incipient wetness impregnation method)

[0085] (1) Test the water absorption rate of the purchased commercial MCM-41 support to determine the amount of deionized water required for impregnation;

[0086] (2) Dissolve 1.66 g of Cu(NO3)2·3H2O in deionized water, and stir or ultrasonically treat until completely dissolved;

[0087] (3) Add the MCM-41 support to the mixed solution, stir and ultrasonically treat to make the impregnation uniform, and let it stand overnight at room temperature;

[0088] After drying overnight in an oven, the dried material is placed in a tubular furnace and calcined at 600 °C for 7 h, and taken out after cooling to room temperature to obtain a CuO / MCM-41 with a theoretical loading of 21%.

[0089] Comparative Example 2

[0090] Preparation method of CuO / Co·SiO2 adsorbent (this material is synthesized by incipient wetness impregnation method)

[0091] (1) Test the water absorption rate of the purchased commercial SiO2 carrier to determine the amount of deionized water required for impregnation;

[0092] (2) Dissolve 1.66 g of Cu(NO3)2·3H2O in deionized water and stir or sonicate until completely dissolved;

[0093] (3) Add the SiO2 carrier to the mixed solution, stir and sonicate to make the impregnation uniform, and let it stand overnight at room temperature;

[0094] (4) After drying overnight in the oven, put the dried material into a tube furnace and calcine it at 600 °C for 7 h. After cooling to room temperature, take it out to obtain CuO / Co·SiO2 with a theoretical loading of 21% (where "Co" represents the commercially purchased material Commercial).

[0095] Comparative Example 3

[0096] Disperse 60 mg of nano-CuO cores in a mixed solvent of 220 mL of deionized water and ethanol (volume ratio of ethanol / water = 1.75 / 1), and alternately stir and sonicate until uniform. Then, add 3 g of cetyltrimethylammonium bromide (CTAB) and 0.9 mL of triethanolamine. Stir the mixture evenly, and then add 1.8 mL of tetraethyl orthosilicate (TEOS) to the solution. The solution is stirred overnight at room temperature, and the resulting solid is separated by centrifugation, washed with a co-solvent of acetone-ethanol, and dried overnight in the oven. Finally, put the dried material into a tube furnace and calcine it at 600 °C for 7 h. After cooling to room temperature, take it out to obtain a CuO@Sp·SiO2 core-shell sphere adsorbent with a theoretical loading of 11%.

[0097] Effect verification

[0098] Effect Example 1 (three-component reaction gas)

[0099] Sieve the core-shell CuO@Sp·SiO2 adsorbent prepared in Example 1 to 40-60 mesh, pack it in a fixed-bed reactor, with the packed mass of the adsorbent being 0.3 g. Introduce sulfur-containing pollutants with a total sulfur content of 1000 ppm of CH3SH, CH3SSCH3, and H2S (where CH3SH∶CH3SSCH3∶H2S = 3∶2∶7) into the fixed-bed reactor simultaneously, control the total gas flow rate to be 40 mL / min, the adsorption system pressure to be atmospheric pressure, and the adsorption temperature to be 40 °C, and conduct an activity evaluation experiment for the adsorption and removal of sulfur-containing pollutants in a three-component system.

[0100] Figure 1For the adsorption activities of the adsorbents prepared in Example 1, Comparative Example 1, and Comparative Example 2 under a three-component reaction gas (CH3SH, CH3SSCH3, and H2S), as can be seen from the figure, in the three-component system, the CuO@Sp·SiO2 adsorbent in Example 1 exhibited significant desulfurization performance for CH3SH. At the initial stage of the experiment, its desulfurization activity reached 100%. For the removal of CH3SSCH3, the CuO@Sp·SiO2 adsorbent could continuously and effectively adsorb CH3SSCH3, showing remarkable stability;

[0101] The activities of CuO / MCM-41 in Comparative Example 1 for CH3SH and H2S started to decline after the start of the experiment, and the activity was much lower than that of the adsorbent in Example 1; moreover, although the CuO / MCM-41 adsorbent had the best removal activity for CH3SSCH3, its stability was lower than that of the adsorbent in Example 1.

[0102] The desulfurization efficiency of CuO@Co·SiO2 in Comparative Example 2 for CH3SH and H2S decreased rapidly after the start of the experiment; and the CuO@Co·SiO2 adsorbent showed a phenomenon opposite to that of Example 1 in the removal effect of CH3SSCH3, specifically: at the beginning, the removal rate of CH3SSCH3 was negative, which might be due to its lack of adsorption activity for CH3SSCH3 and the catalytic oxidation of CH3SH to CH3SSCH3, and then its removal efficiency increased, but it was still much lower than that in Example 1.

[0103] In addition, in the three-component system, the desulfurization performance of the adsorbent prepared in Comparative Example 3 for CH3SH was only 60% at the initial stage of the experiment, a decrease of about 40% compared with the adsorbent in Example 1. At the same time, the adsorbent in Comparative Example 3 could continuously adsorb CH3SSCH3, showing the same pattern as the adsorbent in Example 1.

[0104] Effect Example 2 (two-component reaction gas)

[0105] The difference between the experimental process of the adsorption and removal activity evaluation of sulfur-containing pollutants in the two-component system in Effect Example 2 and that in Effect Example 1 was that the two-component reaction gas was replaced with the three-component reaction gas, and the CH3SH and CH3SSCH3 with a total sulfur content of 1000 ppm (where CH3SH∶CH3SSCH3 = 9∶1).

[0106] Figure 2 For the adsorption activities of the adsorbents prepared in Example 1, Comparative Example 1, and Comparative Example 2 under a two-component reaction gas (CH3SH, CH3SSCH3), from Figure 2It can be seen that in the binary component system, the CuO@Sp·SiO2 adsorbent in Example 1 still exhibits remarkable high desulfurization performance for CH3SSCH3. In addition, the CuO@Sp·SiO2 adsorbent also has remarkable high desulfurization performance for CH3SH, showing 100% desulfurization activity at the beginning of the experiment;

[0107] The removal stability of the CuO / MCM-41 adsorbent in Comparative Example 1 for CH3SSCH3 is much lower than that of the adsorbent in Example 1; and the adsorption rate for the removal of CH3SH drops rapidly to below 25% at the beginning;

[0108] For the desulfurization efficiency of CuO@Co·SiO2 in Comparative Example 2 for CH3SH, it drops rapidly after the start of the experiment; the removal rate for CH3SSCH3 at the beginning is negative, similar to that in Effect Example 1, and its desulfurization efficiency is much lower than that of the adsorbent in Example 1.

[0109] In addition, in the binary component system, the desulfurization performance of the adsorbent prepared in Comparative Example 3 for CH3SSCH3 drops by about 35% compared with the adsorbent in Example 1. The desulfurization performance of the adsorbent for CH3SH is 64% at the beginning of the experiment, and the performance is much lower than 100% of Example 1.

[0110] Effect Example 3 (single-component hydrogen sulfide reaction gas)

[0111] The difference between the evaluation experiment process of the adsorption and removal of sulfur-containing pollutants in the single-component system in Effect Example 3 and that in Effect Example 1 is that the single-component reaction gas is replaced with a three-component reaction gas, and the total sulfur content is 1000 ppm of H2S.

[0112] Figure 3 For the adsorption activities of the adsorbents prepared in Example 1, Comparative Example 1, and Comparative Example 2 under the single-component reaction gas (H2S), from Figure 3 It can be seen that in the single-component system, the CuO@Sp·SiO2 adsorbent in Example 1 has remarkable high desulfurization performance for H2S and has 100% desulfurization activity at the beginning stage of the experiment;

[0113] The CuO / MCM-41 adsorbent in Comparative Example 1 is rapidly deactivated after the start of the experiment, and its desulfurization efficiency is much lower than that of the adsorbent in Example 1;

[0114] For the desulfurization efficiency of CuO@Co·SiO2 for H2S, it drops rapidly after the start of the experiment. When its activity drops below 20%, the desulfurization efficiency of the adsorbent in Example 1 is still 100%, and the desulfurization efficiency of CuO@Co·SiO2 is much lower than that of the adsorbent in Example 1.

[0115] In addition, in the single-component system, the desulfurization performance of the adsorbent prepared in Comparative Example 3 for H2S was only 70% at the beginning of the experiment, which was significantly lower than that of Example 1, with a decrease of about 30%.

[0116] The above are only the preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the technical field of the present application within the technical scope disclosed in the present application should be covered by the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. Application of a core-shell CuO@Sp·SiO2 adsorbent in adsorptive removal of multi-component sulfur-containing pollutants, characterized in that, The preparation process of the core-shell CuO@Sp·SiO2 adsorbent includes the following steps: Dissolve nano-CuO, a reducing agent, a templating agent, and a surfactant in water, then add a silicon source, and then stir and calcine to obtain a CuO@Sp·SiO2 adsorbent with nano-CuO as the core and spherical mesoporous SiO2 as the shell; Among them, the mass ratio of the nano-CuO to the silicon source is (0.05~0.3)∶1; The reducing agent includes ethanol; The templating agent includes cetyltrimethylammonium bromide and / or cetyltrimethylammonium chloride; The surfactant is one of triethanolamine or diethanolamine; The silicon source includes tetraethyl orthosilicate; The conditions during the calcination process are as follows: Calcine at 500~600 °C for 6~10 h; The multi-component sulfur-containing pollutants include three components or two components; Among them, the three-component sulfur-containing pollutants are: CH3SH, CH3SSCH3, and H2S; The two-component sulfur-containing pollutants are: CH3SH and CH3SSCH; The average diameter of the core in a single spherical core-shell CuO@Sp·SiO2 adsorbent is 51~52 nm, and the average diameter of a single sphere is 137~138 nm.

2. Use of a core-shell CuO@Sp·SiO2 adsorbent according to claim 1 in the adsorption and removal of multi-component sulfur-containing pollutants, characterized in that, The time required for the stirring is 16~24 h.

3. Use of a core-shell CuO@Sp·SiO2 adsorbent according to claim 1 in the adsorption and removal of multi-component sulfur-containing pollutants, characterized in that, It includes the following steps: Pass the sulfur-containing pollutant gas into a reactor containing the core-shell CuO@Sp·SiO2 adsorbent, and perform adsorption and removal under normal temperature and pressure conditions.

4. Use of a core-shell CuO@Sp·SiO2 adsorbent according to claim 1 in adsorptive removal of multi-component sulfur-containing pollutants, characterized in that, The ratio relationship between the total sulfur concentration of the sulfur-containing pollutant gas and the dosage of the core-shell CuO@Sp·SiO2 adsorbent is: 1000 ppm∶(0.2~0.3) g; the inlet flow rate of the sulfur-containing pollutant gas is 30~40 mL / min.

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