Active manganese formaldehyde decomposition tablet and preparation method thereof

Abstract

The present application relates to the technical field of formaldehyde removal, and provides active manganese formaldehyde decomposition tablets and a preparation method thereof, which comprise active manganese mixed glue and a carrier; the active manganese mixed glue comprises the following raw materials in parts by weight: 20-30 parts of active manganese catalyst, 4-8 parts of binder, 0.5-3 parts of dispersing agent, and 50-70 parts of deionized water; and the carrier is PET non-woven fabric. The active manganese formaldehyde decomposition tablets provided by the present application have the performance of efficiently decomposing and removing formaldehyde.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of formaldehyde removal, in particular to an active manganese formaldehyde decomposition sheet and a preparation method thereof. BACKGROUND

[0002] Formaldehyde is one of the most common indoor air pollutants, which mainly comes from decoration materials, furniture, tobacco smoke, etc. If long-term exposure to low concentrations of formaldehyde may cause respiratory diseases, allergic reactions, and even increase the risk of cancer. Therefore, in recent years, with the gradual enhancement of people's environmental protection and health awareness, more and more formaldehyde removal products have been developed by researchers and put into the market.

[0003] At present, the removal of formaldehyde mainly falls into two aspects, one is adsorption, and the other is decomposition. In the aspect of adsorption, the common ones are green plants and activated carbon, etc., but the adsorption capacity of these substances for formaldehyde is limited. Compared with the adsorption method, the decomposition method can completely remove formaldehyde. The decomposition method mainly relies on the addition of catalysts to achieve the decomposition of formaldehyde. Generally, noble metals and metal oxides are selected. The noble metals are generally selected from Pd, Au, Ag, Pt, etc. However, the use cost of these substances is high. Among the metal oxides, researchers found that the catalyst with manganese dioxide as the main component, i.e. active manganese, has unique catalytic performance and can achieve efficient decomposition of formaldehyde, converting it into harmless carbon dioxide and water, effectively reducing the concentration of indoor organic pollutants such as formaldehyde, and creating a healthy and comfortable living and working environment for people. Based on this, in recent years, the concept of active manganese decomposition sheet has been gradually proposed.

[0004] Although manganese dioxide has the above characteristics of high cost performance and good formaldehyde decomposition effect, the catalytic activity and stability of manganese dioxide itself still need to be improved. For example, the catalytic activity of manganese dioxide is greatly affected by temperature, and the reaction rate is slow at room temperature, which is difficult to meet the demand of rapid removal of formaldehyde. In addition, the active sites of manganese dioxide are easily covered by the reaction products, resulting in deactivation of the catalyst.

[0005] Patent CN 116371359 A discloses a formaldehyde adsorbent containing active manganese and a preparation method thereof. The formaldehyde adsorbent prepared by the application comprises activated manganese powder carbon, powder carbon, a binder and water. The application utilizes the catalytic oxidation function of manganese oxide to decompose formaldehyde and cooperates with the physical adsorption of activated carbon to effectively improve the removal rate of formaldehyde. However, the application does not solve the problem of insufficient catalytic activity and stability of the prepared manganese dioxide itself, and still has certain application limitations.

[0006] Therefore, there is an urgent need in the market for an active manganese formaldehyde decomposition sheet with high efficient formaldehyde decomposition and removal performance. SUMMARY

[0007] In view of the problems in the prior art, the active manganese mixed glue and the carrier are combined to form the active manganese formaldehyde decomposition sheet, wherein the active manganese catalyst designed and synthesized is used as the main component in the active manganese mixed glue, and the binder and the dispersing agent are combined to improve the catalytic activity and stability of the traditional active manganese, so that the active manganese formaldehyde decomposition sheet has the performance of efficiently decomposing and removing formaldehyde.

[0008] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0009] The present application provides an active manganese formaldehyde decomposition sheet, comprising active manganese mixed glue and a carrier.

[0010] According to the weight fraction, the active manganese mixed glue comprises the following raw materials: 20-30 parts of active manganese catalyst, 4-8 parts of binder, 0.5-3 parts of dispersing agent, and 50-70 parts of deionized water.

[0011] The carrier is PET non-woven fabric.

[0012] The PET non-woven fabric is PET needle-punched non-woven fabric or PET spun-bonded non-woven fabric.

[0013] In some embodiments of the present application, the preparation method of the active manganese catalyst comprises the following steps:

[0014] (1) KMnO4 is added to a reaction container, deionized water is added, stirring is performed, concentrated sulfuric acid and methanol are sequentially added, stirring is performed at 90-100 DEG C for 50-70 min, and a suspension is obtained for standby use;

[0015] (2) Tetramethylammonium chloride and deionized water are mixed, stirring is performed, the suspension of step (1) is added, stirring is performed until a precipitate is generated, suction filtration is performed, centrifugation is performed, drying is performed, and product 1 is obtained for standby use;

[0016] (3) Product 1 of step (2) is taken, deionized water is added, stirring is performed, an aqueous Fe(NO3)3 solution is added, stirring is performed, filtration is performed, washing is performed, drying is performed, and product 2 is obtained for standby use;

[0017] (4) Waste graphite powder is wet ball-milled, the solid and product 2 of step (3) are mixed, ball-milling is performed, washing is performed, drying is performed, and the active manganese catalyst is obtained.

[0018] In some embodiments of the present application, the mass ratio of KMnO4 and tetramethylammonium chloride is 1:(3-3.7).

[0019] Preferably, the mass ratio of KMnO4 and tetramethylammonium chloride is 1:3.33.

[0020] In some embodiments of the present application, in step (3), the mass ratio of product 1 to Fe(NO3)3 in the aqueous solution of Fe(NO3)3 is 1:(0.5-0.6).

[0021] Preferably, in step (3), the mass ratio of product 1 to Fe(NO3)3 in the aqueous solution of Fe(NO3)3 is 1:0.54.

[0022] In some embodiments of the present application, in step (4), the mass ratio of product 2 to the solid is 1:(0.1-0.3).

[0023] Preferably, in step (4), the mass ratio of product 2 to the solid is 1:0.2.

[0024] Active manganese refers to a catalytic material with manganese dioxide as the main component. Manganese oxide accelerates the reaction of formaldehyde and oxygen to decompose formaldehyde into carbon dioxide and water, thereby achieving the purpose of completely removing formaldehyde. However, the catalytic activity and stability of manganese dioxide itself still need to be improved, which limits its ability to decompose formaldehyde at room temperature.

[0025] The applicant first prepared a manganese dioxide suspension using KMnO4 as the raw material, then introduced tetramethylammonium chloride for modification, embedded ammonium cations into the interlayer of manganese dioxide, made it act as an interlayer "pillar" to expand the interlayer spacing of manganese dioxide, thereby increasing the active sites of manganese dioxide, and improved the catalytic activity of manganese dioxide. In addition, the uniform distribution of ammonium cations in the manganese dioxide layer can further improve the stability of manganese dioxide and improve its ability to decompose formaldehyde at room temperature. Further, the applicant doped Fe into product 1, which replaced K in the interlayer of manganese dioxide to reconstruct the interlayer active sites, thereby improving the oxygen activity. In addition, there is a certain interaction force between Fe and ammonium cations, which further improves the stability of the whole catalyst. Finally, the applicant uses widely available waste graphite as the raw material, and the applicant processes it with a simple ball milling process to greatly improve its specific surface area, which improves the formaldehyde adsorption capacity of the graphite powder. The product 2 and the graphite powder are compounded to obtain a catalyst, which synergistically improves the formaldehyde removal performance and stability of the active manganese catalyst, and the obtained active manganese catalyst has high formaldehyde removal efficiency at room temperature. 3+ 3+ In addition, there is a certain interaction force between Fe and ammonium cations, which further improves the stability of the whole catalyst. Finally, the applicant uses widely available waste graphite as the raw material, and the applicant processes it with a simple ball milling process to greatly improve its specific surface area, which improves the formaldehyde adsorption capacity of the graphite powder. The product 2 and the graphite powder are compounded to obtain a catalyst, which synergistically improves the formaldehyde removal performance and stability of the active manganese catalyst, and the obtained active manganese catalyst has high formaldehyde removal efficiency at room temperature.

[0026] In some embodiments of the present application, the active manganese mixed glue further comprises 1-5 parts of quartz stone powder by weight.

[0027] In some embodiments of the present application, the average particle size of the quartz stone powder is 3-10 μm.

[0028] ​The application adds a certain amount of quartz stone micro powder with a specific particle size to the active manganese mixed glue, and the active manganese mixed glue has good dispersity and uniformity, can fill the micro pores of the active manganese mixed glue, make the structure of the material more dense, improve the overall strength and stability of the active manganese formaldehyde decomposition sheet, and further prolong the service life of the active manganese decomposition sheet; and the addition of a certain amount of quartz stone micro powder can also reduce the viscosity of the formaldehyde decomposition sheet to a certain extent, improve the fluidity, facilitate the extrusion and molding of the product, and improve the production efficiency.

[0029] In some embodiments of the application, the binder is sodium carboxymethyl cellulose or polyvinyl alcohol.

[0030] In some embodiments of the application, the dispersant is polyethylene glycol.

[0031] Preferably, the polyethylene glycol is PEG 600 or PEG 2000.

[0032] Another aspect of the application also provides a preparation method of the active manganese formaldehyde decomposition sheet as described in the above technical solutions, and the preparation method comprises the following steps:

[0033] S1, mixing an active manganese catalyst, quartz stone micro powder, a binder, a dispersant and deionized water, stirring to obtain an active manganese mixed glue for standby use;

[0034] S2, coating the active manganese mixed glue of step S1 on a carrier to a thickness of 0.2-0.4 mm, extruding, drying at 100-120 DEG C for 2-3 h, cutting after molding, to obtain an active manganese formaldehyde decomposition sheet.

[0035] In the step S2, the pressure of extrusion is 0.5-2.0 MPa, and the time is 30-60 s.

[0036] Compared with the prior art, the application has the following beneficial effects:

[0037] (1) The active manganese formaldehyde decomposition sheet is prepared by combining the active manganese mixed glue and the carrier, wherein the active manganese catalyst designed and synthesized is the main component in the active manganese mixed glue, and the binder and the dispersant are combined, the active manganese formaldehyde decomposition sheet has the performance of efficiently decomposing and removing formaldehyde, and can be widely applied to the technical field of removing formaldehyde.

[0038] (2) The application designs an active manganese catalyst, first introduces tetramethylammonium chloride for modification, embeds the ammonium cation into the interlayer of manganese dioxide to improve the catalytic activity and stability of the manganese dioxide; further, the applicant introduces Fe 3+Doping, Fe replaces interlayer K to reconfigure interlayer active sites, thereby improving oxygen activity; finally, the applicant uses waste graphite as a carrier raw material and processes it by ball milling to increase its specific surface area, thereby improving the formaldehyde adsorption capacity of the graphite powder, and the above product is compounded with the waste graphite powder after wet ball milling to obtain a catalyst, which synergistically improves the formaldehyde removal performance and stability of the active manganese catalyst as a whole, so that the obtained active manganese catalyst has high formaldehyde removal efficiency at room temperature.

[0039] (3) The application adds a certain amount of quartz stone micro powder with a specific particle size, which has good dispersity and uniformity, can fill the micro pores of the active manganese mixed glue, makes the structure of the material more dense, improves the overall strength and stability of the active manganese formaldehyde decomposition sheet, and further prolongs the service life of the active manganese decomposition sheet. DETAILED DESCRIPTION

[0040] The application will be described below in conjunction with specific embodiments. It should be noted that the following examples are examples of the application and are only used to illustrate the application, but not to limit the application. Other combinations and various modifications within the concept of the application can be made without departing from the main idea or scope of the application.

[0041] In the following examples and comparative examples, the compounds monomers and related reagents used except for the active manganese catalyst can be purchased from the market, wherein the PET non-woven fabric is PET needle-punched non-woven fabric or PET spun-bond non-woven fabric, both of which are purchased from Jiangxi Haorui Industrial Material Co., Ltd.; the average particle size of the quartz stone micro powder is 1 μm, 5 μm or 10 μm; the carboxymethyl cellulose sodium is purchased from Zibo Daoqin New Material Co., Ltd.; the polyvinyl alcohol is purchased from Yuyao Yibai Plastic Co., Ltd.; and the polyethylene glycol is PEG 600 or PEG 2000.

[0042] Preparation Example 1

[0043] The synthesis method of the active manganese catalyst A includes the following steps:

[0044] (1) 12 g of KMnO4 was added to a reaction container, 500 ml of deionized water was added, stirred for 1 h, 7.5 g of 98 wt% concentrated sulfuric acid and 50 g of methanol were sequentially added, stirred at 95℃ for 60 min, and a suspension was obtained for standby use;

[0045] (2) 40 g of tetramethylammonium chloride and 500 ml of deionized water were mixed, stirred for 1 h, and then the suspension of step (1) was added, stirred until precipitation was generated, suction filtered, centrifuged, and vacuum dried at 60℃ for 12 h to obtain product 1 for standby use;

[0046] (3) Take 12 g of the product 1 of step (2), add 200 ml of deionized water, stir for 1 h, add 13.5 ml of 2 mol / L Fe(NO3)3 aqueous solution (in three equal amounts), stir for 24 h, filter, wash with deionized water for 3 times, and vacuum dry at 60℃ for 24 h to obtain product 2 for standby use;

[0047] (4) Wet ball mill 5 g of waste graphite powder at 600 r / min for 2 h, take 2 g of solid and mix with 10 g of product 2 of step (3), ball mill for 30 min, wash with deionized water for 3 times, and vacuum dry at 60℃ for 24 h to obtain active manganese catalyst A.

[0048] Preparation Example 2

[0049] Active manganese catalyst B, the specific implementation manner is the same as that of active manganese catalyst A, except that the mass of tetramethylammonium chloride in step (2) is replaced by 34 g.

[0050] Preparation Example 3

[0051] Active manganese catalyst C, the specific implementation manner is the same as that of active manganese catalyst A, except that the volume of Fe(NO3)3 aqueous solution in step (3) is replaced by 8 ml.

[0052] Preparation Example 4

[0053] Active manganese catalyst D, the specific implementation manner is the same as that of active manganese catalyst A, except that the mass of solid in step (4) is replaced by 0.8 g.

[0054] Example 1

[0055] An active manganese formaldehyde decomposition sheet includes an active manganese mixed glue and a carrier.

[0056] The active manganese formaldehyde decomposition sheet includes the following raw materials in parts by weight: 25 parts of active manganese catalyst A, 3 parts of quartz stone micro powder, 6 parts of sodium carboxymethyl cellulose, 1.5 parts of PEG 2000, and 60 parts of deionized water.

[0057] The carrier is PET needle-punched non-woven fabric.

[0058] The average particle size of the quartz stone micro powder is 5 μm.

[0059] The preparation method of the active manganese formaldehyde decomposition sheet in the embodiment includes the following steps:

[0060] S1, mix active manganese catalyst A, quartz stone micro powder, sodium carboxymethyl cellulose, PEG 2000 and deionized water, stir uniformly, and obtain active manganese mixed glue for standby use.

[0061] S2, the active manganese mixed glue of step S1 is coated on the PET needle punched non-woven fabric to a thickness of 0.3mm, extruded at 1MPa for 40s, dried at 110℃ for 2.5h, and cut after molding, to obtain the active manganese formaldehyde decomposition sheet.

[0062] Example 2

[0063] An active manganese formaldehyde decomposition sheet, comprising an active manganese mixed glue and a carrier;

[0064] The active manganese formaldehyde decomposition sheet comprises the following raw materials in parts by weight: active manganese catalyst A 20 parts, quartz stone micro powder 1 part, polyvinyl alcohol 4 parts, PEG 600 0.5 parts, and deionized water 50 parts;

[0065] The carrier is a PET spun-bonded non-woven fabric.

[0066] The average particle size of the quartz stone micro powder is 5μm.

[0067] The preparation method of the active manganese formaldehyde decomposition sheet in the embodiment comprises the following steps:

[0068] S1, mix the active manganese catalyst A, the quartz stone micro powder, the polyvinyl alcohol, the PEG 600 and the deionized water, and stir uniformly to obtain the active manganese mixed glue for standby use;

[0069] S2, the active manganese mixed glue of step S1 is coated on the PET needle punched non-woven fabric to a thickness of 0.3mm, extruded at 1MPa for 40s, dried at 110℃ for 2.5h, and cut after molding, to obtain the active manganese formaldehyde decomposition sheet.

[0070] Example 3

[0071] An active manganese formaldehyde decomposition sheet, comprising an active manganese mixed glue and a carrier;

[0072] The active manganese formaldehyde decomposition sheet comprises the following raw materials in parts by weight: active manganese catalyst A 20 parts, quartz stone micro powder 1 part, polyvinyl alcohol 4 parts, PEG 600 0.5 parts, and deionized water 50 parts;

[0073] The carrier is a PET needle punched non-woven fabric.

[0074] The average particle size of the quartz stone micro powder is 5μm.

[0075] The preparation method of the active manganese formaldehyde decomposition sheet in the embodiment comprises the following steps:

[0076] S1, mix the active manganese catalyst A, the quartz stone micro powder, the polyvinyl alcohol, the PEG 600 and the deionized water, and stir uniformly to obtain the active manganese mixed glue for standby use;

[0077] S2, the active manganese mixed glue of step S1 is coated on the PET needle punched non-woven fabric to a thickness of 0.4mm, extruded at 2.0MPa for 30s, dried at 120℃ for 2h, cut after molding, to obtain the active manganese formaldehyde decomposition sheet.

[0078] Example 4

[0079] An active manganese formaldehyde decomposition sheet, comprising an active manganese mixed glue and a carrier;

[0080] The active manganese formaldehyde decomposition sheet comprises the following raw materials in parts by weight: active manganese catalyst A 25 parts, sodium carboxymethyl cellulose 6 parts, PEG 2000 1.5 parts, deionized water 60 parts;

[0081] The carrier is a PET needle punched non-woven fabric.

[0082] The average particle size of the quartz stone powder is 5μm.

[0083] The preparation method of the active manganese formaldehyde decomposition sheet in the embodiment comprises the following steps:

[0084] S1, mix the active manganese catalyst A, sodium carboxymethyl cellulose, PEG 2000 and deionized water, stir uniformly, and obtain the active manganese mixed glue for standby use;

[0085] S2, the active manganese mixed glue of step S1 is coated on the PET needle punched non-woven fabric to a thickness of 0.3mm, extruded at 1MPa for 40s, dried at 110℃ for 2.5h, cut after molding, to obtain the active manganese formaldehyde decomposition sheet.

[0086] Example 5

[0087] The embodiment provides an active manganese formaldehyde decomposition sheet and a preparation method thereof, and the specific implementation manner is the same as that in embodiment 1, and the difference lies in that the average particle size of the quartz stone powder is 1μm.

[0088] Example 6

[0089] The embodiment provides an active manganese formaldehyde decomposition sheet and a preparation method thereof, and the specific implementation manner is the same as that in embodiment 1, and the difference lies in that the average particle size of the quartz stone powder is 15μm.

[0090] Example 7

[0091] The embodiment provides an active manganese formaldehyde decomposition sheet and a preparation method thereof, and the specific implementation manner is the same as that in embodiment 1, and the difference lies in that the active manganese catalyst B is used to replace the active manganese catalyst A.

[0092] Example 8

[0093] This embodiment provides an active manganese formaldehyde decomposition sheet and a preparation method thereof, and the specific embodiment is the same as that of embodiment 1, except that the active manganese catalyst C is used to replace the active manganese catalyst A.

[0094] Example 9

[0095] This embodiment provides an active manganese formaldehyde decomposition sheet and a preparation method thereof, and the specific embodiment is the same as that of embodiment 1, except that the active manganese catalyst D is used to replace the active manganese catalyst A.

[0096] Example 10

[0097] This embodiment provides an active manganese formaldehyde decomposition sheet and a preparation method thereof, and the specific embodiment is the same as that of embodiment 1, except that the manganese dioxide is used to replace the active manganese catalyst A.

[0098] Performance test

[0099] The formaldehyde removal effect of the active manganese formaldehyde decomposition sheets of embodiments 1-10 is tested, and the test results are shown in Table 1.

[0100] The active manganese formaldehyde decomposition sheets in the above embodiments are cut into 10 cm x 10 cm, and each one is placed in a 10 m 3 L formaldehyde closed chamber with an initial concentration of 1 mg / m 3 L formaldehyde, and the removal rate of formaldehyde is tested after 24 hours.

[0101] The removal rate of formaldehyde (%) = (initial formaldehyde concentration - 24 h formaldehyde concentration) / initial formaldehyde concentration x 100%

[0102] The formaldehyde detection method is detected according to the method specified in GB / T 18204.26-2000.

[0103] Table 1

[0104]

[0105]

[0106] As shown in Table 1, the active manganese formaldehyde decomposition tablets in Examples 1-3 have high formaldehyde removal rate, i.e. de-aldehyde effect. In Example 4, no quartz stone powder is added, in Examples 5-6, the particle size of the quartz stone powder is changed, which reduces the overall strength and stability of the active manganese formaldehyde decomposition tablets, and further affects the de-aldehyde effect of the active manganese formaldehyde decomposition tablets to a certain extent; in Examples 7-9, the use ratio of tetramethylammonium chloride, Fe(NO3)3 and waste graphite powder in the active manganese catalyst is changed, which reduces the catalytic activity or stability of the active manganese catalyst, and further reduces the de-aldehyde effect of the active manganese formaldehyde decomposition tablets; in Example 10, manganese dioxide is used to replace the active manganese catalyst A in equal amount, which significantly reduces the de-aldehyde effect of the active manganese formaldehyde decomposition tablets.

[0107] The above embodiments are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and implement it, and cannot limit the protection scope of the present application. Any equivalent changes or modifications made according to the spirit and essence of the present application should be covered within the protection scope of the present application.

Claims

1. An active manganese formol-splitting tablet, characterized in that, The active manganese mixed glue comprises an active manganese catalyst, a binder, a dispersing agent and deionized water. The active manganese mixed glue comprises the following ingredients by weight: 20-30 parts of the active manganese catalyst, 4-8 parts of the binder, 0.5-3 parts of the dispersing agent and 50-70 parts of deionized water. The carrier is PET non-woven fabric. The preparation method of the active manganese catalyst comprises the following steps: (1) adding KMnO4 into a reaction container, adding deionized water, stirring, adding concentrated sulfuric acid and methanol in sequence, stirring at 90-100 ℃ for 50-70 min to obtain a suspension for standby use; (2) mixing tetramethylammonium chloride and deionized water, stirring, then adding the suspension of step (1), stirring until precipitation occurs, suction filtering, centrifuging, drying to obtain product 1 for standby use; (3) taking product 1 of step (2), adding deionized water, stirring, adding Fe(NO3)3 aqueous solution, stirring, filtering, washing, drying to obtain product 2 for standby use; (4) wet ball milling the waste graphite powder, mixing the solid and product 2 of step (3), ball milling, washing, drying to obtain the active manganese catalyst; The mass ratio of KMnO4 to tetramethylammonium chloride is 1: (3-3.7); In step (3), the mass ratio of product 1 to Fe(NO3)3 in the Fe(NO3)3 aqueous solution is 1: (0.5-0.6); In step (4), the mass ratio of product 2 to the solid is 1: (0.1-0.3).

2. The active manganese formol decomposition tablet according to claim 1, characterized in that, The active manganese mixed glue further comprises 1-5 parts of quartz stone micro powder by weight.

3. The active manganese formol-splitting tablet according to claim 2, characterized in that The average particle size of the quartz stone micro powder is 3-10 μm.

4. The active manganese formol process tablet according to claim 1, wherein The binder is sodium carboxymethyl cellulose or polyvinyl alcohol.

5. The active manganese formol decomposition tablet according to claim 1, characterized in that, The dispersing agent is polyethylene glycol.

6. A process for the preparation of the active manganese formate decomposing tablet according to any one of claims 2 to 5, characterized in that, The method comprises the following steps: S1, mixing the active manganese catalyst, the quartz stone micro powder, the binder, the dispersing agent and deionized water, stirring to obtain the active manganese mixed glue for standby use; S2, coating the active manganese mixed glue of step S1 on the carrier to a thickness of 0.2-0.4 mm, extruding, drying at 100-120 ℃ for 2-3 h, cutting after molding to obtain the active manganese formaldehyde decomposition sheet.

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