A catalyst for removing volatile impurities and a method for preparing and using the same

Abstract

The application provides a catalyst for removing volatile impurities and a preparation method and application thereof. The catalyst contains a carrier and an active component. The carrier contains silicon-modified manganese oxide, and the active component contains copper oxide. The content of copper oxide in the form of Cu2O in the active component is 10-65 wt%, preferably 15-60 wt%, based on the total weight of the active component. The catalyst has a special active crystal structure, strong oxidizing property and strong adsorbing property, can induce strong chemical adsorption of volatile impurities on the surface of the catalyst and complete catalytic conversion, and thus realizes removal and purification of volatile impurities in air.

Description

Technical Field

[0001] This invention relates to the field of air purification, specifically to a catalyst for removing volatile impurities, its preparation method, and its application. Background Technology

[0002] VOCs include several major categories such as non-methane hydrocarbons (NMHCs), oxygenated organic compounds, halogenated hydrocarbons, nitrogen-containing organic compounds, and sulfur-containing organic compounds. Most VOCs have an unpleasant odor and are toxic, irritating, teratogenic, and carcinogenic. Benzene, toluene, and formaldehyde, in particular, can cause significant harm to human health. Formaldehyde is the most prevalent VOC, ranking second on my country's list of controlled toxic chemicals. Its sources are widespread, including not only wood materials, flooring materials, and paints used in decoration, but also often overlooked cosmetics, cleaning agents, incompletely burned tobacco leaves, and textile fibers. Formaldehyde poses significant health risks. Acute poisoning can cause symptoms such as burning throat, nausea, fatigue, difficulty breathing, and pulmonary edema. Chronic poisoning can lead to symptoms like itchy skin, cough, chest tightness, and shortness of breath. Long-term exposure to low doses of formaldehyde can result in weakened immune function, neurasthenia leading to memory loss, chronic respiratory diseases, and in severe cases, blood disorders, including leukemia. Statistics show that within 1-6 months after renovation, formaldehyde levels in most homes exceed the standard by as much as 80%; even 3 years after renovation, some homes still have formaldehyde levels exceeding the standard by more than 50%. Therefore, the dangers of formaldehyde cannot be ignored, and its control has become a major concern. How to quickly and effectively reduce the harm of formaldehyde to the human body has become an urgent problem to be solved. CN105964289A provides a catalyst for formaldehyde removal at room temperature and its preparation method, which loads Ag-Pt on a tetrabutyl titanate modified support to achieve formaldehyde removal at room temperature; however, the catalyst provided by this method is less economical due to the use of precious metals and does not have the basis for large-scale commercial application.

[0003] CN107983320A provides a method for preparing and applying a dual-functional thin film for formaldehyde removal. It describes the preparation of a thin film using a rare earth element nitrate-modified activated carbon carrier loaded with manganese and an electrostatic filament solution. This thin film simultaneously possesses adsorption and catalytic oxidation functions, thus achieving the effect of formaldehyde removal.

[0004] CN110624403A provides a filter screen for removing formaldehyde and odors. A manganese catalyst is obtained by hydrothermal synthesis of a solution containing manganese, iron and oxalate. The catalyst is then dissolved in a silica sol gel, sprayed onto the filter screen, and dried to achieve the function of removing formaldehyde at room temperature.

[0005] However, the room-temperature formaldehyde removal catalysts provided by the above patents are not suitable for large-scale use due to their poor economic efficiency, complex preparation methods, and poor operability. In the field of residential room-temperature formaldehyde removal, the following basic characteristics are required: firstly, strong formaldehyde removal capability; and secondly, air quality standards requiring that the formaldehyde content in the home environment not exceed 0.1 mg / m³. 3 First, due to the limitations of room temperature formaldehyde removal catalysts, they must have extremely high reactivity to meet the requirements. Second, the catalyst strength must be high, as room temperature formaldehyde removal agents need to be used in adsorption and purification devices in large places such as buildings, office buildings, hospitals, and shopping malls, where the space velocity is high, and the catalyst strength must be able to meet the impact strength requirements under high space velocity. Third, the lifespan must be long, because due to the mechanism, the formaldehyde removal efficiency of formaldehyde removal agents often decreases as the reaction proceeds, and may even become completely ineffective. Therefore, room temperature formaldehyde removal agents must have the ability to be regenerated at room temperature to meet the requirements of long-term use.

[0006] Therefore, in view of the shortcomings of existing technologies, there is an urgent need to provide a catalyst and purification material that can remove volatile impurities such as formaldehyde and toluene from gases, and that has high removal efficiency, high intensity and stable effect. Summary of the Invention

[0007] The purpose of this disclosure is to provide a catalyst with strong oxidizing and adsorption properties, capable of stably removing volatile impurities.

[0008] To achieve the above objectives, this disclosure provides a catalyst for removing volatile impurities, the catalyst comprising a support and an active ingredient, the support comprising silicon-modified manganese oxide, and the active ingredient comprising copper oxide;

[0009] Based on the total weight of the active ingredients, the content of copper oxide in the form of Cu2O in the active ingredients is 10-65 wt%, preferably 15-60 wt%.

[0010] Optionally, based on the dry weight of the catalyst, the content of the support is 70-99.6 wt%, and the content of the active ingredient is 0.4-30 wt%.

[0011] Preferably, based on the dry weight of the catalyst, the content of the support is 90-99 wt%, and the content of the active ingredient is 1-10 wt%.

[0012] Optionally, the manganese oxide is selected from one or more of α-MnO2, β-MnO2, γ-MnO2, MnO, Mn3O4, Mn2O3, naphthoore, busselite, hydroxyl manganite, barium manganite, potassium manganite, and calcium manganite;

[0013] In the silicon-modified manganese oxide, the weight ratio of silicon to manganese is 1:(5-35), preferably 1:(6-30); preferably, the copper oxide also contains CuO.

[0014] Optionally, the catalyst has a BET specific surface area of ​​60-200 m². 2 / g, preferably 80-180m 2 / g; pore volume is 0.3-1.0cm³ 3 / g, preferably 0.4-0.8cm 3 / g.

[0015] Optionally, the volatile impurities include at least one of formaldehyde, toluene, xylene, and methanol.

[0016] On the other hand, this disclosure provides a method for preparing a catalyst for removing volatile impurities, the method comprising the following steps:

[0017] A mixture containing acid, reducing agent, copper source and oxidized manganese source is subjected to hydrothermal reaction to obtain a precipitate, and the precipitate is dried to obtain a dried product;

[0018] The organosilicon modifier is contacted with the dried product for dispersion and in-situ hydrolysis, followed by drying.

[0019] Optionally, the dispersion and in-situ hydrolysis process includes:

[0020] The first material containing the organosilicon modifier, the dried product and the organic solvent is refluxed and heated to obtain a dispersed material, and the dispersed material is contacted with water and / or ethanol.

[0021] Alternatively, the in-situ hydrolysis operation may include: reflux heating a second material containing an organosilicon modifier, the dried product, water, and an organic solvent;

[0022] The amount of organic solvent used is 5-10 parts by weight relative to 1 part by weight of the organosilicon modifier.

[0023] The organic solvent is selected from one or more of toluene, ethanol, ammonia, propanol and cyclohexane; the reflux heating conditions include: reflux temperature of 60-150℃ and reflux time of 4-30h; the drying conditions include: temperature of 80-200℃ and time of 2-30h.

[0024] Optionally, the organosilicon modifier is a silane coupling agent and / or a siloxane coupling agent, the acid is an organic acid and / or an inorganic acid, the reducing agent is an organic acid and / or a reduced manganese source, and the organic acid is one or more selected from oxalic acid and acetic acid, preferably oxalic acid;

[0025] Optionally, the oxidized manganese source is a manganese compound containing heptavalent manganese, preferably selected from one or more of potassium permanganate, potassium manganate, and sodium permanganate;

[0026] The reduced manganese source is a manganese compound containing divalent manganese, preferably selected from one or more of manganese oxalate, manganese acetate, and manganese chloride;

[0027] The copper source is selected from one or more of copper nitrate, copper sulfate and copper chloride, preferably copper sulfate;

[0028] The weight ratio of the oxidized manganese source, acid, reducing agent, copper source and organosilicon modifier is 1:(0.1-3):(0.4-1):(0.05-0.5):(0.01-0.3), preferably 1:(0.5-0.9):(0.1-2):(0.07-0.4):(0.02-0.25).

[0029] Optionally, the conditions for the hydrothermal reaction include: a reaction temperature of 50-200℃, preferably 70-150℃; and a reaction time of 2-48h, preferably 6-24h.

[0030] Optionally, the drying conditions include: a drying temperature of 80-200℃, preferably 100-150℃; and a drying time of 0.5-12h, preferably 1-8h.

[0031] On the other hand, this disclosure provides a purification material for removing volatile impurities, the purification material comprising the above-mentioned catalyst and carrier;

[0032] Optionally, based on the dry weight of the purification material, the content of the catalyst is 5-50 wt%, and the content of the support is 50-95 wt%.

[0033] Preferably, based on the dry weight of the purification material, the content of the catalyst is 10-45 wt%, and the content of the support is 55-90 wt%.

[0034] The carrier is selected from one or more of polyurethane, nonwoven fabric and sponge.

[0035] Optionally, the purification material is prepared by a method comprising the following steps:

[0036] The catalyst is loaded onto the support and dried to obtain the purification material.

[0037] Optionally, the drying conditions include: a drying temperature of 60-80℃ and a drying time of 1-8h.

[0038] Through the above technical solution, this disclosure provides a catalyst for removing volatile impurities, its preparation method and application. The catalyst has a special active crystal structure, strong oxidizing and strong adsorption properties, and can induce volatile impurities to undergo strong chemical adsorption on the catalyst surface and complete catalytic transformation, thereby achieving the removal and purification of volatile impurities in the air.

[0039] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Attached Figure Description

[0040] The accompanying drawings are provided to further illustrate the present disclosure and form part of the specification. They are used together with the following detailed description to explain the present disclosure, but do not constitute a limitation thereof. In the drawings:

[0041] Figure 1 This is a SEM image of catalyst A1 disclosed in this publication.

[0042] Figure 2 This is a TEM image of catalyst A1 disclosed in this publication. Detailed Implementation

[0043] The following provides a detailed description of specific embodiments of this disclosure. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit this disclosure.

[0044] On one hand, this disclosure provides a catalyst for removing volatile impurities, characterized in that the catalyst contains a support and an active ingredient; the support contains silicon-modified manganese oxide, and the active ingredient contains copper oxide;

[0045] Based on the total weight of the active ingredients, the content of copper oxide in the form of Cu2O in the active ingredients is 10-65 wt%, preferably 15-60 wt%.

[0046] In one embodiment, based on the dry weight of the catalyst, the content of the support is 70-99.6 wt%, and the content of the active ingredient is 0.4-30 wt%.

[0047] In a preferred embodiment, the content of the support is 90-99 wt% and the content of the active ingredient is 1-10 wt%, based on the dry weight of the catalyst.

[0048] The inventors of this disclosure unexpectedly discovered that by utilizing the molecular sieve properties and active oxygen storage capacity of silicon-modified manganese oxide, volatile impurities in the air can undergo an oxidation reaction with lattice oxygen in the catalyst at room temperature and pressure, achieving high-precision purification of volatile impurities and obtaining a high conversion rate of volatile impurities. Furthermore, in the silicon-modified manganese oxide, silicon is coated on the surface of the manganese oxide in the form of silicon dioxide, further enhancing the adsorption of impurities by the manganese oxide and improving the removal rate.

[0049] In one embodiment, the manganese oxide is one or more selected from α-MnO2, β-MnO2, γ-MnO2, MnO, Mn3O4, Mn2O3, naphthoore, busselite, hydroxyl manganite, barium manganite, potassium manganite, and calcium manganite.

[0050] In the silicon-modified manganese oxide, the weight ratio of silicon to manganese is 1:(5-35), preferably 1:(6-30);

[0051] The copper oxide also contains CuO.

[0052] In one embodiment, the catalyst has a BET specific surface area of ​​60-200 m². 2 / g, pore volume is 0.3-1.0cm³ 3 / g.

[0053] In a preferred embodiment, the catalyst has a BET specific surface area of ​​80-180 m². 2 / g, pore volume is 0.4-0.8cm³ 3 / g.

[0054] In one embodiment, the volatile impurities include at least one of formaldehyde, toluene, xylene, and methanol.

[0055] On the other hand, this disclosure provides a method for preparing a catalyst for removing volatile impurities, the method comprising the following steps:

[0056] A mixture containing acid, reducing agent, copper source and oxidized manganese source is subjected to hydrothermal reaction to obtain a precipitate, and the precipitate is dried to obtain a dried product;

[0057] The organosilicon modifier is contacted with the dried product for dispersion and in-situ hydrolysis, followed by drying.

[0058] In one embodiment, the dispersion and hydrolysis operation includes: reflux heating a first material containing the organosilicon modifier, the dried product and the organic solvent to obtain a dispersed material, and contacting the dispersed material with water and / or ethanol;

[0059] Alternatively, the in-situ hydrolysis operation may include: reflux heating a second material containing the organosilicon modifier, the dried product, water, and an organic solvent;

[0060] The amount of organic solvent used is 5-10 parts by weight relative to 1 part by weight of the organosilicon modifier.

[0061] The organic solvent is selected from one or more of toluene, ethanol, ammonia, propanol, and cyclohexane;

[0062] The conditions for reflux heating include: reflux temperature of 60-150℃ and reflux time of 4-30h;

[0063] The drying conditions include a temperature of 80-200℃ and a time of 2-30 hours.

[0064] In one embodiment, the organosilicon modifier is a silane coupling agent and / or a siloxane coupling agent, the acid is an organic acid and / or an inorganic acid, the reducing agent is an organic acid and / or a reduced manganese source, and the organic acid is one or more selected from oxalic acid and acetic acid, preferably oxalic acid;

[0065] The oxidized manganese source is a manganese compound containing heptavalent manganese, preferably selected from one or more of potassium permanganate, potassium manganate, and sodium permanganate;

[0066] The reduced manganese source is a manganese compound containing divalent manganese, preferably selected from one or more of manganese oxalate, manganese acetate, and manganese chloride;

[0067] The copper source is selected from one or more of copper nitrate, copper sulfate and copper chloride, preferably copper sulfate;

[0068] The weight ratio of the oxidized manganese source, acid, reducing agent, copper source and organosilicon modifier is 1:(0.4-1):(0.1-3):(0.05-0.5):(0.01-0.3), preferably 1:(0.5-0.9):(0.1-2):(0.07-0.4):(0.02-0.25).

[0069] In one embodiment, the conditions for the hydrothermal reaction include: a reaction temperature of 50-200℃ and a reaction time of 2-48h; the conditions for the drying treatment include: a drying temperature of 80-200℃ and a drying time of 0.5-12h.

[0070] In a preferred embodiment, the conditions for the hydrothermal reaction include: a reaction temperature of 70-150°C and a reaction time of 6-24 hours; the conditions for the drying treatment include: a drying temperature of 100-150°C and a drying time of 1-8 hours.

[0071] On the other hand, this disclosure provides a purification material for removing volatile impurities, the purification material comprising the above-mentioned catalyst and carrier;

[0072] Based on the dry weight of the purification material, the content of the catalyst is 5-50 wt%, and the content of the support is 50-95 wt%.

[0073] In a preferred embodiment, based on the dry weight of the purification material, the content of the catalyst is 10-45 wt%, and the content of the carrier is 55-90 wt%.

[0074] In one embodiment, the carrier is one or more selected from polyurethane, nonwoven fabric and sponge.

[0075] In one embodiment, the purification material is prepared by a method comprising the following steps: loading the catalyst onto the support and drying it to obtain the purification material.

[0076] In one embodiment, the drying conditions include: a drying temperature of 60-80°C and a drying time of 1-8 hours.

[0077] The present disclosure is further described in detail below through examples. All raw materials used in the examples are commercially available.

[0078] The XRD diffractometer used in this disclosure is an XRD-6000 X-ray powder diffractometer (Shimadzu, Japan). The XRD test conditions are: Cu target, Kα rays (wavelength λ = 0.154 nm), tube voltage of 40 kV, tube current of 200 mA, and scanning speed of 10°(2θ) / min.

[0079] The content of the components was determined by X-ray fluorescence spectrometry analysis method RIPP 132-90 (Petrochemical Analysis Methods (RIPP Experimental Methods), edited by Yang Cuiding, Gu Kanying, and Wu Wenhui, Science Press, first edition, September 1990, pp. 371-379).

[0080] The SEM used in this disclosure is a Hitachi S-4800.

[0081] The TEM used in this disclosure is a Tecnai G2 F20 S-TWIN high-resolution transmission electron microscope.

[0082] The BET specific surface area (microporous specific surface area) of the catalyst was measured using the nitrogen-purified BET specific surface area method.

[0083] The pore volume was determined using the standard method of GB / T 5816-1995.

[0084] The strength of the catalytic material was tested using a strength tester.

[0085] Preparation Example 1

[0086] Preparation of the catalyst: 33.7 g of potassium permanganate was dissolved in 400 g of deionized water and heated and stirred to form a potassium permanganate solution; 85.64 g of oxalic acid was dissolved in 260 g of deionized water and stirred evenly; 10.22 g of copper nitrate was dissolved in 150 g of deionized water and stirred evenly; the ratio of n(Mn):n(oxalic acid):n(Cu) was 0.21:0.95:0.04. The above three solutions were mixed, the pH was adjusted to 2, and the reaction was carried out at 130℃ for 24 h. The resulting brown precipitate was filtered and washed several times with deionized water until the pH of the washing solution was 7. The solid product was then dried at 120℃ for 8 h to prepare the 3% CuO-MnOx catalyst A1.

[0087] Silicon modification: 5.26g of trimethylchlorosilane (TMCS) was selected as the modifier, and 20g of 3% CuO-MnO was added. x Catalyst A1 was dispersed in 100 mL of 5% TMCS toluene solution, stirred and refluxed at 90 °C for 12 h, washed multiple times with ethanol and distilled water, and dried at 110 °C for 12 h to obtain Si-modified copper-manganese material, namely catalyst A1. The BET specific surface area, pore volume and catalyst strength are shown in Table 2.

[0088] Molding: 1.5g of catalyst A1 was dispersed in 5g of deionized water, impregnated on 5g of polyurethane cotton, dried at 60℃ for 1h, and dried at 80℃ for 6h to prepare purification filter element X1.

[0089] Preparation Example 2

[0090] The catalytic material was prepared using the same steps as in Example 1, except that 20.44 g of copper nitrate was used as the copper salt, and the CuO content was different, resulting in a composition of 6% CuO-MnO. x .

[0091] Silicon modification: 6.88g of octyltrimethoxysilane (OTMS) was selected as the modifier, and 50g of 9% CuO-MnO was added. x The catalyst was dispersed in an anhydrous ethanol solution containing 5% ammonia and stirred at 60°C for 12 h. After washing with anhydrous ethanol to neutralize the solution and remove excess OTMS from the surface, the catalyst was dried at 110°C for 12 h to obtain silane-modified copper-manganese material, which is catalyst A2. The BET specific surface area, pore volume and catalyst strength are shown in Table 2.

[0092] Molding: The purification material X2 was prepared using the same steps as in Example 1, except that the content of the catalyst material was different. 3g of catalyst A2 was dispersed in 5g of deionized water and impregnated on 5g of polyurethane cotton.

[0093] Preparation Example 3

[0094] Preparation of catalytic materials: The copper-manganese materials were prepared using the same steps as in Preparation Example 2.

[0095] Silicon modification: Silicon-modified A3 was prepared in the same manner as in Example 2, except that the organosilicon element was different. 3.12g of tetraethyl orthosilicate was selected as the organosilicon to prepare silicon-modified copper-manganese catalyst A3. The BET specific surface area, pore volume and catalyst strength are shown in Table 2.

[0096] Molding: Catalyst material X3 was prepared in the same manner as in Example 1, except that the content of the catalyst material was different. 3.8g of catalyst A3 was dispersed in 5g of deionized water and impregnated on 5g of polyurethane cotton.

[0097] Preparation Example 4

[0098] Preparation of the catalytic material: 6.34 g of potassium permanganate was dissolved in 60 g of deionized water, heated and stirred to form a potassium permanganate solution, and 10 mL of glacial acetic acid was added and stirred evenly. 8.65 g of manganese acetate solution and 2.11 g of copper sulfate were mixed to form a solution and stirred evenly (n(Mn:n(Cu)=10:1)). The two solutions were mixed, the pH was adjusted to less than 3, and the reaction was carried out at 120℃ for 12 h. The resulting brown precipitate was filtered and washed several times with deionized water until the pH of the washing solution was 7. The solid product was then dried at 120℃ for 4 h to prepare a copper-manganese material, which was 3% CuO-MnOx.

[0099] Silicon modification: 1.26 g of trimethylchlorosilane (TMCS) was selected as the modifier. 20 g of catalyst A4 was dispersed in 100 mL of a 5% (w / w) TMCS toluene solution, and the mixture was stirred and refluxed at 90 °C for 12 h. The mixture was then washed multiple times with ethanol and distilled water, followed by 3% CuO-MnO4. x The TMCS of the catalyst was dried at 110℃ for 12h to obtain Si-modified copper-manganese material, namely catalyst A4. The BET specific surface area, pore volume and catalyst strength are shown in Table 2.

[0100] Molding: The purification material X4 was prepared using the same steps as in Preparation Example 1, except that PET nonwoven fabric was selected as the carrier.

[0101] Preparation of Comparative Example 1

[0102] Preparation of 10% MnO-10% ZnO / Al2O3 by impregnation method

[0103] Alumina supports were impregnated with manganese nitrate and zinc nitrate to prepare 10% MnO-10% ZnO / Al2O3 catalyst D2. The BET specific surface area, pore volume and catalyst strength of catalyst D2 are shown in Table 2.

[0104] Test Example 1

[0105] This test example is used to determine the purification effect of catalysts A1-A4 and D1 on formaldehyde in the air.

[0106] 2 mL of the catalysts from Preparation Examples 1-4 and Comparative Examples 1-2 were weighed and placed in a fixed-bed reactor. Then, air containing formaldehyde (formaldehyde concentration of 10 ppm, N2 concentration of 71%, and O2 concentration of 29% in the carrier) was introduced into the fixed-bed reactor along with the feed gas after passing through a mass flow meter. The reaction was carried out at room temperature and atmospheric pressure, with a volume hourly space velocity of 20,000 h⁻¹. -1 After the catalyst undergoes a formaldehyde desorption reaction, it is calcined at 300℃ for 2 hours in 2% O2-N2 with a controlled temperature ramp rate of 1℃ / min to achieve lattice oxygen replenishment and catalyst regeneration.

[0107] The mixed gas after the reaction is passed into the exhaust gas absorption tank. After testing and confirming that it meets environmental protection requirements, it can be further processed or vented.

[0108] Table 1. Physicochemical Characterization Indicators of Catalysts

[0109]

[0110]

[0111] Table 2

[0112] catalyst <![CDATA[BET surface area / (cm 3 / g)]]> <![CDATA[Pore volume / (cm 3 / g)]]> A1 99 0.68 A2 107 0.65 A3 91 0.54 A4 110 0.58 D1 58 0.23

[0113] Table 2. Test results of formaldehyde purification reaction

[0114]

[0115] As can be seen from Tables 1 and 2, the catalyst provided in this disclosure has a special crystal structure and suitable pore size, with a BET specific surface area of ​​60-200 m². 2 / g, pore volume is 0.3-1.0cm³ 3 / g, after silicon modification and molding, silica covers the surface of the catalyst, which greatly improves the adsorption strength of the catalyst for volatile impurities in the air. When used to purify formaldehyde, it can achieve high-precision purification at room temperature and pressure. Its purification precision is significantly higher than that of comparative example 1. Moreover, the catalyst preparation method is simple and has good repeatability, which is conducive to industrial promotion.

[0116] Test Example 2

[0117] This test example is used to determine the effect of purification materials X1-X4 in removing impurities from the air. The test method is the same as that in test example 1, as shown in Table 3.

[0118] Table 3 Formaldehyde purification test results of purifiers X1-X4

[0119]

[0120] As shown in Table 3, the catalyst provided in this disclosure, after being molded, forms a purification material that has a good removal effect on volatile impurities in the air.

[0121] Test Example 3

[0122] In this test example, the sterilization and purification effects of purification materials X1-X4 were determined according to GB21551.2-2010 "Special requirements for antibacterial, sterilization and purification functions and antibacterial materials of household and similar electrical appliances". The results are shown in Table 4.

[0123] Table 4 GB21551.2-2010 Test of Sterilization Performance of Purifying Agents

[0124]

[0125]

[0126] The preferred embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.

[0127] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.

[0128] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.

Claims

1. A catalyst for removing volatile impurities, characterized in that, The catalyst contains a support and an active ingredient; the support contains silicon-modified manganese oxide, and the active ingredient contains copper oxide. Based on the total weight of the active ingredients, the content of copper oxide in the form of Cu2O in the active ingredients is 10-65 wt%. In the silicon-modified manganese oxide, the weight ratio of silicon to manganese is 1:(5-35). The catalyst has a BET specific surface area of ​​60-200 m². 2 / g, pore volume is 0.3-1.0cm³ 3 / g.

2. The catalyst according to claim 1, wherein, Based on the dry weight of the catalyst, the content of the support is 70-99.6 wt%, and the content of the active ingredient is 0.4-30 wt%.

3. The catalyst according to claim 2, wherein, Based on the total weight of the active ingredients, the content of copper oxide in the form of Cu2O in the active ingredients is 15-60 wt%; Based on the dry weight of the catalyst, the content of the support is 90-99 wt%, and the content of the active ingredient is 1-10 wt%.

4. The catalyst according to claim 1, wherein, The manganese oxide is selected from one or more of α-MnO2, β-MnO2, γ-MnO2, MnO, Mn3O4, Mn2O3, naphthoore, busselite, hydroxyl manganite, barium manganite, potassium manganite, and calcium manganite. In the silicon-modified manganese oxide, the weight ratio of silicon to manganese is 1:(5-35). The copper oxide also contains CuO.

5. The catalyst according to claim 4, wherein, In the silicon-modified manganese oxide, the weight ratio of silicon to manganese is 1:(6-30).

6. The catalyst according to claim 1, wherein, The catalyst has a BET specific surface area of ​​80-180 m². 2 / g; pore volume is 0.4-0.8cm³ 3 / g.

7. The catalyst according to claim 1, wherein, The volatile impurities include at least one of formaldehyde, toluene, xylene, and methanol.

8. A method for preparing the catalyst for removing volatile impurities according to any one of claims 1-7, characterized in that, The method includes the following steps: A mixture containing acid, reducing agent, copper source and oxidized manganese source is subjected to hydrothermal reaction to obtain a precipitate, and the precipitate is dried to obtain a dried product; The organosilicon modifier is contacted with the dried product for dispersion and in-situ hydrolysis, followed by drying.

9. The method according to claim 8, wherein, The dispersion and in-situ hydrolysis operations include: reflux heating a first material containing the organosilicon modifier, the dried product and the organic solvent to obtain a dispersed material, and contacting the dispersed material with water and / or ethanol. Alternatively, the in-situ hydrolysis operation may include: reflux heating a second material containing an organosilicon modifier, the dried product, water, and an organic solvent; The amount of organic solvent used is 5-10 parts by weight relative to 1 part by weight of the organosilicon modifier. The organic solvent is selected from one or more of toluene, ethanol, propanol, and cyclohexane; The conditions for reflux heating include: reflux temperature of 60-150℃ and reflux time of 4-30h; The drying conditions include a temperature of 80-200℃ and a time of 2-30 hours.

10. The method according to claim 8, wherein, The organosilicon modifier is a silane coupling agent and / or a siloxane coupling agent, the acid is an organic acid and / or an inorganic acid, the reducing agent is an organic acid and / or a reduced manganese source, and the organic acid is one or more selected from oxalic acid and acetic acid; The oxidized manganese source is a manganese compound containing heptavalent manganese; The reduced manganese source is a manganese compound containing divalent manganese; The copper source is selected from one or more of copper nitrate, copper sulfate, and copper chloride; The weight ratio of the oxidized manganese source, acid, reducing agent, copper source, and organosilicon modifier is 1:(0.4-1):(0.1-3):(0.05-0.5):(0.01-0.3). The conditions for the hydrothermal reaction include: a reaction temperature of 50-200℃ and a reaction time of 2-48h; The drying conditions include: a drying temperature of 80-200℃ and a drying time of 1-8 hours.

11. The method according to claim 10, wherein, The organic acid is oxalic acid, and the oxidized manganese source is one or more selected from potassium permanganate, potassium manganate and sodium permanganate. The reduced manganese source is selected from one or more of manganese oxalate, manganese acetate and manganese chloride; The copper source is copper sulfate; The weight ratio of the oxidized manganese source, acid, reducing agent, copper source, and organosilicon modifier is 1:(0.5-0.9):(0.1-2):(0.07-0.4):(0.02-0.25). The conditions for the hydrothermal reaction include: a reaction temperature of 70-150℃ and a reaction time of 6-24h; The drying conditions include: a drying temperature of 100-150℃ and a drying time of 1-8 hours.

12. A purification material for removing volatile impurities, characterized in that, The purification material comprises the catalyst and carrier as described in any one of claims 1-7; Based on the dry weight of the purification material, the content of the catalyst is 5-50 wt%, and the content of the support is 50-95 wt%. The carrier is selected from one or more of polyurethane, nonwoven fabric and sponge.

13. The purification material according to claim 12, wherein, Based on the dry weight of the purification material, the content of the catalyst is 10-45 wt%, and the content of the carrier is 55-90 wt%.

14. The purification material according to claim 13, wherein, The purification material is prepared by a method comprising the following steps: The catalyst is loaded onto the support and dried to obtain the purification material. The drying conditions include: a drying temperature of 60-80℃ and a drying time of 1-8 hours.

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