Preparation method and application of formaldehyde remover for artificial board

Abstract

The invention discloses a preparation method and application of a formaldehyde removal agent for artificial boards. First, graphene oxide is ultrasonically dispersed in deionized water, and the pH is adjusted to alkaline to obtain a graphene oxide dispersion; zinc nitrate, cuprous nitrate, nano copper powder and sodium citrate are ultrasonically dispersed in deionized water to obtain a metal ion dispersion; then the metal ion dispersion is added to the graphene oxide dispersion, stirred evenly, subjected to hydrothermal reaction, filtered to obtain a solid, and calcined in a nitrogen atmosphere to obtain a graphene composite material; then melamine and cerium oxalate are used as raw materials to prepare a graphene-like phase carbon nitride loaded with cerium oxide; finally, the graphene composite material, the graphene-like phase carbon nitride loaded with cerium oxide, polyethylene glycol 200 and deionized water are uniformly mixed to obtain the formaldehyde removal agent obtained by the invention. The formaldehyde removal agent obtained by the invention is easy to use and has a good formaldehyde removal effect.

Description

Technical Field

[0001] The invention relates to a formaldehyde remover, in particular to a preparation method and application of a formaldehyde remover for artificial boards, belonging to the technical field of formaldehyde removal. Background Art

[0002] With the development of society and the improvement of living standards, people have a higher and higher demand for interior decoration, and artificial boards are commonly used materials for interior decoration. Artificial boards are made of wood or other non-wood plants as raw materials, separated into various unit materials through certain mechanical processing, and glued with adhesives or other additives to form boards or molded products. The adhesive commonly used in the production process of artificial boards is urea-formaldehyde resin adhesive, which is a composite of urea and formaldehyde. The advantages of urea-formaldehyde resin adhesive are low production cost and easy use. The disadvantage is that it is easy to continuously release formaldehyde and is the main source of indoor formaldehyde pollution. Therefore, it is very necessary to remove formaldehyde from artificial boards.

[0003] There are mainly the following methods for removing formaldehyde from artificial boards:

[0004] 1. The finishing method can inhibit the overflow of formaldehyde in the artificial board, but it will cause new formaldehyde pollution, making a large amount of formaldehyde on the surface of the artificial board;

[0005] 2. Chemical method: Although the short-term effect is obvious, chemicals will cause new pollution;

[0006] 3. Hot ammonia method, high cost, long processing time, and harsh working environment;

[0007] 4. Vacuum / negative pressure method: the processing time is long, the equipment and processing costs are high, it is easy to generate new pollution, and the working environment is poor.

[0008] Patent CN106808543B discloses a method for removing formaldehyde from artificial boards using microwaves, comprising the following steps:

[0009] (1) Raw material pretreatment; (2) Binder preparation; (3) Mixing and stirring; (4) Paving and calendering; (5) Hot pressing and curing;

[0010] (6) Microwave formaldehyde removal. Adding microwave absorbing heat-generating powder to the binder has a microwave absorbing heat-generating effect. During the microwave treatment of artificial boards, it can rapidly increase the temperature inside and outside the artificial boards, accelerate the release of formaldehyde, and prevent the artificial boards from deforming. However, the addition of microwave absorbing heat-generating powder will inevitably affect the performance of artificial boards, and the essence is that formaldehyde is directly released, causing environmental pollution.

[0011] Patent CN105365013B discloses a method for treating formaldehyde in artificial boards, wherein the artificial boards are sent into a closed conveyor, oxygen anions are introduced, and the boards are exposed to an electrostatic field or a high magnetic field for 1 to 25 minutes, so that the oxygen anions penetrate into the artificial boards, and then high-energy particle collision, ultrasound, ultraviolet rays, infrared rays or near-infrared rays are used for 1 to 30 minutes to induce self-oxidation of formaldehyde into formic acid, carbon dioxide and water. After the treatment, the formaldehyde release of the artificial boards reaches the level of natural wood. This patented technology has certain requirements for equipment, and the process is relatively complicated, so it is difficult to promote it on a large scale.

[0012] Patent CN114870591B discloses a piperazine-based composite material formaldehyde remover and its preparation method, which contains the following raw materials by weight: 2-20 parts of deionized water, 0.1-5 parts of piperazine, 0.01-5 parts of functional molecules, and 0.1-10 parts of carriers. The formaldehyde removal ability of the formaldehyde remover obtained by this patent technology is average. Summary of the invention

[0013] The purpose of the present invention is to overcome the deficiencies of the prior art and to provide a method for preparing and applying a formaldehyde remover for artificial panels.

[0014] To achieve the above object, the present invention adopts the following technical solutions:

[0015] The present invention provides a method for preparing a formaldehyde remover for artificial boards, and the specific steps are as follows:

[0016] (1) firstly ultrasonically dispersing graphene oxide in deionized water, adjusting the pH to alkaline, and obtaining a graphene oxide dispersion; ultrasonically dispersing zinc nitrate, cuprous nitrate, nano copper powder, and sodium citrate in deionized water, and obtaining a metal ion dispersion;

[0017] (2) adding the metal ion dispersion to the graphene oxide dispersion, stirring evenly, performing a hydrothermal reaction, filtering out a solid, and calcining in a nitrogen atmosphere to obtain a graphene composite material;

[0018] (3) then preparing graphene-like carbon nitride loaded with cerium oxide using melamine and cerium oxalate as raw materials;

[0019] (4) Finally, the graphene composite material, the graphene-like carbon nitride loaded with cerium oxide, polyethylene glycol 200 and deionized water are evenly mixed to obtain the formaldehyde removal agent.

[0020] Preferably, in step (1), the process conditions for ultrasonic dispersion are: 300-400W ultrasonic dispersion for 30-40 minutes.

[0021] Preferably, in step (1), the pH is adjusted to 9-10 using a 0.3-0.5 mol / L sodium carbonate aqueous solution.

[0022] Preferably, in step (1), when preparing the graphene oxide dispersion, the usage ratio of graphene oxide to deionized water is 1 mg: 3-5 mL.

[0023] Preferably, in step (1), when preparing the metal ion dispersion, the molar ratio of zinc nitrate, cuprous nitrate, nano copper powder and sodium citrate is 1:0.3-0.5:0.3-0.4:2-2.2; the amount of deionized water used is 25-30 times the mass of sodium citrate; the zinc nitrate is zinc nitrate hexahydrate, and the cuprous nitrate is cuprous nitrate hemihydrate (pentahydrate).

[0024] Preferably, in step (2), the volume ratio of the metal ion dispersion to the graphene oxide dispersion is 1:1.

[0025] Preferably, in step (2), the process conditions of the hydrothermal reaction are: hydrothermal reaction at 120-130° C. for 8-10 hours.

[0026] Preferably, in step (2), the calcination process conditions are: firstly increase the temperature to 250-300°C at 5-7°C / min, keep the temperature for 20-30 minutes, then increase the temperature to 400-450°C at 2-3°C / min, and keep the temperature for 2-3 hours.

[0027] Preferably, the specific method of step (3) is: firstly, melamine and cerium oxalate are mixed in a mass ratio of 1:0.01-0.02 and ground for 5-7 minutes, and then heat-treated at 620-650° C. for 3-4 hours to obtain the product.

[0028] Preferably, in step (4), the mass ratio of the graphene composite material, the graphene-like carbon nitride loaded with cerium oxide, polyethylene glycol 200 and deionized water is 2-3:1-2:1.5-2:100.

[0029] The present invention also provides a formaldehyde remover for artificial panels, which is obtained by the above-mentioned preparation method.

[0030] The present invention also provides application of the above-mentioned formaldehyde remover in processing of artificial boards.

[0031] Beneficial effects of the present invention:

[0032] The present invention first ultrasonically disperses graphene oxide in deionized water, adjusts the pH to alkalinity, and obtains a graphene oxide dispersion; ultrasonically disperses zinc nitrate, cuprous nitrate, nano copper powder and sodium citrate in deionized water to obtain a metal ion dispersion; then adds the metal ion dispersion to the graphene oxide dispersion, stirs evenly, performs a hydrothermal reaction, filters out solids, and bakes in a nitrogen atmosphere to obtain a graphene composite material; then uses melamine and cerium oxalate as raw materials to prepare graphene-like carbon nitride loaded with cerium oxide; finally, the graphene composite material, the graphene-like carbon nitride loaded with cerium oxide, polyethylene glycol 200 and deionized water are uniformly mixed to obtain a aldehyde removal agent. The aldehyde removal agent obtained by the present invention is easy to use and has a good aldehyde removal effect.

[0033] The present invention has a very good adsorption effect on formaldehyde emitted from artificial boards through the synergistic effect of the graphene composite material and the graphene-like carbon nitride loaded with cerium oxide, and can catalyze and promote the decomposition of formaldehyde under visible light, thereby achieving efficient formaldehyde removal.

[0034] The graphene composite material of the present invention comprises graphene, zinc oxide, copper oxide, cuprous oxide and the like. The graphene-like carbon nitride phase loaded with cerium oxide has a graphene-like structure, has good adsorption properties and contains cerium oxide. Through the synergistic effect of the above oxides and the graphene structure, the number of photogenerated electrons and holes increases, the separation efficiency is high, and it has a very good photocatalytic effect under the action of visible light, thereby achieving efficient removal of formaldehyde. DETAILED DESCRIPTION

[0035] The present invention is further described below in conjunction with embodiments. It should be noted that the following description is only for explaining the present invention and does not limit its contents.

[0036] Embodiment 1:

[0037] A method for preparing a formaldehyde remover for artificial panels, comprising the following specific steps:

[0038] (1) First, 1 g of graphene oxide was ultrasonically dispersed in 3 L of deionized water, and the pH was adjusted to 9 using a 0.3 mol / L sodium carbonate aqueous solution to obtain a graphene oxide dispersion; 0.01 mol of zinc nitrate hexahydrate (2.975 g), 0.003 mol of cuprous nitrate hemihydrate (pentahydrate) (0.699 g), 0.003 mol of nano-copper powder (0.191 g) and 0.02 mol of sodium citrate (5.160 g) were ultrasonically dispersed in 129 mL of deionized water to obtain a metal ion dispersion;

[0039] (2) adding the metal ion dispersion to the graphene oxide dispersion, stirring evenly, performing a hydrothermal reaction, filtering out a solid, and calcining in a nitrogen atmosphere to obtain a graphene composite material;

[0040] (3) then preparing graphene-like carbon nitride loaded with cerium oxide using melamine and cerium oxalate as raw materials;

[0041] (4) Finally, 2 g of the graphene composite material, 1 g of the graphene-like carbon nitride loaded with cerium oxide, 1.5 g of polyethylene glycol 200 and 100 mL of deionized water were mixed evenly to obtain the formaldehyde removal agent.

[0042] In step (1), the process conditions for ultrasonic dispersion are: 300W ultrasonic dispersion for 30 minutes.

[0043] In step (2), the volume ratio of the metal ion dispersion to the graphene oxide dispersion is 1:1.

[0044] The process conditions of the hydrothermal reaction are: 120° C. hydrothermal reaction for 8 hours.

[0045] The calcination process conditions are: first increase the temperature to 250°C at 5°C / min, keep it at that temperature for 20 minutes, then increase the temperature to 400°C at 2°C / min, and keep it at that temperature for 2 hours.

[0046] The specific method of step (3) is: firstly, melamine and cerium oxalate are mixed in a mass ratio of 1:0.01 and ground for 5 minutes, and then heat-treated at 620° C. for 3 hours to obtain the product.

[0047] Embodiment 2:

[0048] A method for preparing a formaldehyde remover for artificial panels, comprising the following specific steps:

[0049] (1) First, 1 g of graphene oxide was ultrasonically dispersed in 5 L of deionized water, and the pH was adjusted to 10 using a 0.5 mol / L sodium carbonate aqueous solution to obtain a graphene oxide dispersion; 0.01 mol of zinc nitrate hexahydrate (2.975 g), 0.005 mol of cuprous nitrate hemi(pentahydrate) (1.165 g), 0.004 mol of nano-copper powder (0.254 g) and 0.022 mol of sodium citrate (5.676 g) were ultrasonically dispersed in 141.9 mL of deionized water to obtain a metal ion dispersion;

[0050] (2) adding the metal ion dispersion to the graphene oxide dispersion, stirring evenly, performing a hydrothermal reaction, filtering out a solid, and calcining in a nitrogen atmosphere to obtain a graphene composite material;

[0051] (3) then preparing graphene-like carbon nitride loaded with cerium oxide using melamine and cerium oxalate as raw materials;

[0052] (4) Finally, 3 g of the graphene composite material, 2 g of the graphene-like carbon nitride loaded with cerium oxide, 2 g of polyethylene glycol 200 and 100 mL of deionized water were mixed evenly to obtain the formaldehyde removal agent.

[0053] In step (1), the process conditions for ultrasonic dispersion are: 400W ultrasonic dispersion for 40 minutes.

[0054] In step (2), the volume ratio of the metal ion dispersion to the graphene oxide dispersion is 1:1.

[0055] The process conditions of the hydrothermal reaction are: hydrothermal reaction at 130° C. for 10 hours.

[0056] The calcination process conditions are: first increase the temperature to 300°C at 7°C / min, keep warm for 30 minutes, then increase the temperature to 450°C at 3°C / min, and keep warm for 3 hours.

[0057] The specific method of step (3) is: firstly, melamine and cerium oxalate are mixed in a mass ratio of 1:0.02 and ground for 7 minutes, and then heat-treated at 650° C. for 4 hours to obtain the product.

[0058] Embodiment 3:

[0059] A method for preparing a formaldehyde remover for artificial panels, comprising the following specific steps:

[0060] (1) First, 1 g of graphene oxide was ultrasonically dispersed in 3 L of deionized water, and the pH was adjusted to 9 using a 0.5 mol / L sodium carbonate aqueous solution to obtain a graphene oxide dispersion; 0.01 mol of zinc nitrate hexahydrate (2.975 g), 0.003 mol of cuprous nitrate hemi(pentahydrate) (0.699 g), 0.004 mol of nano-copper powder (0.254 g) and 0.02 mol of sodium citrate (5.160 g) were ultrasonically dispersed in 141.9 mL of deionized water to obtain a metal ion dispersion;

[0061] (2) adding the metal ion dispersion to the graphene oxide dispersion, stirring evenly, performing a hydrothermal reaction, filtering out a solid, and calcining in a nitrogen atmosphere to obtain a graphene composite material;

[0062] (3) then preparing graphene-like carbon nitride loaded with cerium oxide using melamine and cerium oxalate as raw materials;

[0063] (4) Finally, 2 g of the graphene composite material, 2 g of the graphene-like carbon nitride loaded with cerium oxide, 1.5 g of polyethylene glycol 200 and 100 mL of deionized water were mixed evenly to obtain the formaldehyde removal agent.

[0064] In step (1), the process conditions of ultrasonic dispersion are: 300W ultrasonic dispersion for 40 minutes.

[0065] In step (2), the volume ratio of the metal ion dispersion to the graphene oxide dispersion is 1:1.

[0066] The process conditions of the hydrothermal reaction are: 130° C. hydrothermal reaction for 8 hours.

[0067] The calcination process conditions are: first increase the temperature to 250°C at 7°C / min, keep warm for 30 minutes, then increase the temperature to 450°C at 2°C / min, and keep warm for 2 hours.

[0068] The specific method of step (3) is: firstly, melamine and cerium oxalate are mixed in a mass ratio of 1:0.02 and ground for 5 minutes, and then heat-treated at 650° C. for 3 hours to obtain the product.

[0069] Embodiment 4:

[0070] A method for preparing a formaldehyde remover for artificial panels, comprising the following specific steps:

[0071] (1) First, 1 g of graphene oxide was ultrasonically dispersed in 5 L of deionized water, and the pH was adjusted to 10 using a 0.3 mol / L sodium carbonate aqueous solution to obtain a graphene oxide dispersion; 0.01 mol of zinc nitrate hexahydrate (2.975 g), 0.005 mol of cuprous nitrate hemi(pentahydrate) (1.165 g), 0.003 mol of nano-copper powder (0.191 g) and 0.022 mol of sodium citrate (5.676 g) were ultrasonically dispersed in 129 mL of deionized water to obtain a metal ion dispersion;

[0072] (2) adding the metal ion dispersion to the graphene oxide dispersion, stirring evenly, performing a hydrothermal reaction, filtering out a solid, and calcining in a nitrogen atmosphere to obtain a graphene composite material;

[0073] (3) then preparing graphene-like carbon nitride loaded with cerium oxide using melamine and cerium oxalate as raw materials;

[0074] (4) Finally, 3 g of the graphene composite material, 1 g of the graphene-like carbon nitride loaded with cerium oxide, 2 g of polyethylene glycol 200 and 100 mL of deionized water were mixed evenly to obtain the formaldehyde removal agent.

[0075] In step (1), the process conditions for ultrasonic dispersion are: 400W ultrasonic dispersion for 35 minutes.

[0076] In step (2), the volume ratio of the metal ion dispersion to the graphene oxide dispersion is 1:1.

[0077] The process conditions of the hydrothermal reaction are: hydrothermal reaction at 120° C. for 10 hours.

[0078] The calcination process conditions are: first increase the temperature to 300°C at 5°C / min, keep warm for 20 minutes, then increase the temperature to 400°C at 3°C / min, and keep warm for 3 hours.

[0079] The specific method of step (3) is: firstly, melamine and cerium oxalate are mixed in a mass ratio of 1:0.01 and ground for 7 minutes, and then heat-treated at 620° C. for 4 hours to obtain the product.

[0080] Comparative Example 1

[0081] A method for preparing a formaldehyde remover for artificial panels, comprising the following specific steps:

[0082] (1) firstly prepare graphene-like carbon nitride loaded with cerium oxide using melamine and cerium oxalate as raw materials;

[0083] (2) Then, 1 g of graphene-like carbon nitride loaded with cerium oxide, 1.5 g of polyethylene glycol 200 and 100 mL of deionized water were mixed evenly to obtain the formaldehyde removal agent.

[0084] The specific method of step (1) is: firstly, melamine and cerium oxalate are mixed in a mass ratio of 1:0.01 and ground for 5 minutes, and then heat-treated at 620° C. for 3 hours to obtain the product.

[0085] Comparative Example 2

[0086] A method for preparing a formaldehyde remover for artificial panels, comprising the following specific steps:

[0087] (1) First, 1 g of graphene oxide was ultrasonically dispersed in 3 L of deionized water, and the pH was adjusted to 9 using a 0.3 mol / L sodium carbonate aqueous solution to obtain a graphene oxide dispersion; 0.01 mol of zinc nitrate hexahydrate (2.975 g), 0.003 mol of cuprous nitrate hemihydrate (pentahydrate) (0.699 g), 0.003 mol of nano-copper powder (0.191 g) and 0.02 mol of sodium citrate (5.160 g) were ultrasonically dispersed in 129 mL of deionized water to obtain a metal ion dispersion;

[0088] (2) adding the metal ion dispersion to the graphene oxide dispersion, stirring evenly, performing a hydrothermal reaction, filtering out a solid, and calcining in a nitrogen atmosphere to obtain a graphene composite material;

[0089] (3) Finally, 2 g of the graphene composite material, 1.5 g of polyethylene glycol 200 and 100 mL of deionized water were mixed evenly to obtain the formaldehyde removal agent.

[0090] In step (1), the process conditions for ultrasonic dispersion are: 300W ultrasonic dispersion for 30 minutes.

[0091] In step (2), the volume ratio of the metal ion dispersion to the graphene oxide dispersion is 1:1.

[0092] The process conditions of the hydrothermal reaction are: 120° C. hydrothermal reaction for 8 hours.

[0093] The calcination process conditions are: first increase the temperature to 250°C at 5°C / min, keep it at that temperature for 20 minutes, then increase the temperature to 400°C at 2°C / min, and keep it at that temperature for 2 hours.

[0094] Test example

[0095] The formaldehyde removers obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were respectively used for formaldehyde removal treatment of artificial boards. The specific method is as follows: the formaldehyde remover is added to nitrocellulose primer (purchased from Zhengzhou Qingteng Paint Co., Ltd.) in a mass ratio of 1:5 (solid content). The mixture is stirred and evenly mixed, and evenly sprayed on the surface of the artificial board. The mixture is cured and dried to form a coating with a thickness of 0.1 μm.

[0096] The artificial board treated with the above-mentioned formaldehyde removal agent was placed under natural light conditions, and the formaldehyde release after different placement times was tested using the desiccator method. The test results are shown in Table 1.

[0097] Table 1. Formaldehyde emission test results of artificial boards after formaldehyde removal treatment

[0098]

[0099]

[0100] It can be seen from Table 1 that the formaldehyde removal agents obtained in Examples 1 to 4 have a very good formaldehyde removal effect on artificial boards and are effective for a long time.

[0101] In Comparative Example 1, the graphene composite material is omitted, and in Comparative Example 2, the graphene-like carbon nitride loaded with cerium oxide is omitted, and the formaldehyde removal effect (including the long-term formaldehyde removal effect) is significantly deteriorated, indicating that the graphene composite material and the graphene-like carbon nitride loaded with cerium oxide act synergistically to improve the formaldehyde removal effect on the artificial board.

[0102] Although the above describes the specific implementation methods of the present invention, it does not limit the scope of protection of the present invention. Based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection of the present invention.

Claims

1. A method for preparing a formaldehyde remover for artificial boards, characterized in that: The specific steps are as follows: (1) firstly ultrasonically dispersing graphene oxide in deionized water, adjusting the pH to alkaline, and obtaining a graphene oxide dispersion; ultrasonically dispersing zinc nitrate, cuprous nitrate, nano copper powder, and sodium citrate in deionized water, and obtaining a metal ion dispersion; (2) adding the metal ion dispersion to the graphene oxide dispersion, stirring evenly, performing a hydrothermal reaction, filtering out the solid, and calcining in a nitrogen atmosphere to obtain a graphene composite material; (3) then preparing graphene-like carbon nitride loaded with cerium oxide using melamine and cerium oxalate as raw materials; (4) finally, the graphene composite material, the graphene-like carbon nitride loaded with cerium oxide, polyethylene glycol 200 and deionized water are uniformly mixed to obtain the formaldehyde removal agent; The specific method of step (3) is: firstly, melamine and cerium oxalate are mixed in a mass ratio of 1:0.01-0.02 and ground for 5-7 minutes, and then heat-treated at 620-650° C. for 3-4 hours to obtain the product.

2. The preparation method according to claim 1, characterized in that: In step (1), the process conditions of ultrasonic dispersion are: 300-400W ultrasonic dispersion for 30-40 minutes.

3. The preparation method according to claim 1, characterized in that: In step (1), when preparing the graphene oxide dispersion, the ratio of graphene oxide to deionized water is 1 mg: 3-5 mL; When preparing the metal ion dispersion, the molar ratio of zinc nitrate, cuprous nitrate, nano copper powder and sodium citrate is 1:0.3-0.5:0.3-0.4:2-2.2; the amount of deionized water used is 25-30 times the mass of sodium citrate.

4. The preparation method according to claim 1, characterized in that: In step (2), the volume ratio of the metal ion dispersion to the graphene oxide dispersion is 1:

1.

5. The preparation method according to claim 1, characterized in that: In step (2), the process conditions of the hydrothermal reaction are: hydrothermal reaction at 120-130° C. for 8-10 hours.

6. The preparation method according to claim 1, characterized in that: In step (2), the calcination process conditions are: firstly increase the temperature to 250-300°C at 5-7°C / min, keep the temperature for 20-30 minutes, then increase the temperature to 400-450°C at 2-3°C / min, and keep the temperature for 2-3 hours.

7. The preparation method according to claim 1, characterized in that: In step (4), the mass ratio of the graphene composite material, the graphene-like carbon nitride loaded with cerium oxide, polyethylene glycol 200 and deionized water is 2-3:1-2:1.5-2:

100.

8. A formaldehyde remover for artificial boards, characterized in that: The invention is obtained by the preparation method according to any one of claims 1 to 7.

9. Use of the formaldehyde remover according to claim 8 in the processing of artificial boards.

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