CN115041199A - Green odorless formaldehyde purifying agent and preparation method thereof - Google Patents
Green odorless formaldehyde purifying agent and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of formaldehyde purification, and particularly relates to a green and odorless formaldehyde purifying agent and a preparation method thereof. The preparation method comprises the following steps: (1) dissolving bismuth salt, samarium salt, ytterbium salt and ferric salt in a hydrochloric acid solution to obtain a mixed solution, then adding diatomite into the mixed solution, and uniformly stirring; then dropwise adding an alkali solution to adjust the pH value to 9-11; then transferring the mixture into a hydrothermal reaction kettle for hydrothermal reaction, naturally cooling the mixture to room temperature, filtering, washing and drying the mixture to obtain a product A; (2) dissolving a molybdenum source, an iron salt, a copper salt and a sulfur source in deionized water to form a solution, stirring, adding the product A prepared in the step (1) into the solution, continuing stirring, transferring the obtained solution into a reaction kettle for reaction, cooling to room temperature, filtering, washing and drying to obtain the formaldehyde purifying agent. The formaldehyde purifying agent prepared by the invention has excellent adsorption capacity and removal capacity on formaldehyde, and has excellent application prospect.
Description
Technical Field
The invention belongs to the technical field of formaldehyde purification. More particularly relates to a green odorless formaldehyde purifying agent and a preparation method thereof.
Background
With the rapid development of social economy, the indoor volatile organic pollution problem is more and more concerned by researchers. Functional wooden material such as indoor floor, cabinet and wall board, textile and wallPaper, adhesives, paints, coatings and the like generally slowly and continuously release gas pollutants such as formaldehyde, aromatic compounds and the like in daily use, wherein the formaldehyde pollution is common, and the formaldehyde pollution is regarded as an air killer in the living environment and threatens the physical and psychological health of people. According to the 'sanitary standard for formaldehyde in room air' in China, the allowable mass concentration of formaldehyde in the room air is not higher than 0.08mg/m 3 . When the mass concentration of the formaldehyde gas in the room exceeds 0.1mg/m 3 In time, the room usually has peculiar smell, and the human body has uncomfortable feeling; the environment containing a large amount of formaldehyde gas pollutants can cause respiratory diseases, and severe leukemia, chronic poisoning and even death can be induced. Therefore, the method has important significance in treating indoor formaldehyde gas pollutants.
Common formaldehyde removal techniques include adsorption, catalytic oxidation, photocatalysis, plant absorption, and plasma. Wherein, the plant absorption method has the defects of poor adsorption effect and undetermined timeliness; the plasma method has the problems that an ion source generating device is needed, the energy consumption is high in the actual operation process, the method is not suitable for household use, and the like, and the practicability is not high. At present, the commonly used technology for purifying formaldehyde in gas mainly comprises an adsorption method and a heterogeneous catalysis method (catalytic oxidation and photocatalysis). The adsorption method has the advantages of simple operation, low price, wide application range, recyclability, no energy consumption and the like, is widely used for treating low-concentration formaldehyde pollution, and the photocatalysis technology has the advantages of simple process, easily controlled operation conditions, low energy consumption, thorough pollutant degradation and the like, and is considered to be an environment-friendly new technology with good development prospect.
The surface of the nano mineral material such as clay silicate mineral and the like has negative charges due to the lattice substitution effect, and the end surface contains abundant silicon/aluminum hydroxyl; two-dimensional layered mineral materials such as montmorillonite have expandable interlaminar domains. The natural nano mineral material has stronger surface and interface reaction activity, is directly used as an adsorbent to treat formaldehyde pollution, and has the advantages of low price, simple operation and the like.
CN109647418A discloses a preparation method of a foamed nickel supported samarium doped titanium oxide photocatalyst, which adopts a solvothermal method, takes foamed nickel as a substrate and TiO 2 Is used as a matrix and is doped with a small amount of Sm 3+ Preparing foam nickel base Sm 3+ Doped TiO 2 2 The photocatalyst is applied to purification and treatment of VOCs gases such as indoor formaldehyde, and the formaldehyde purification rate is expected to be more than 90% in a short time.
CN114570348A discloses a titanium dioxide-based nano composite photocatalyst for photocatalytic degradation by visible light irradiation and application thereof. The preparation method of the titanium dioxide-based nano composite photocatalyst comprises the following steps: dissolving a titanium-containing precursor into a solvent to obtain a titanium-containing solution, adding a silicon-containing compound, uniformly stirring, and finally adding rare earth salt and dissolving to obtain a mixed solution; and carrying out hot-pressing reaction on the mixed solution under a closed condition, cooling to room temperature after the reaction is finished, carrying out suction filtration to obtain a solid, and drying the solid to obtain the titanium dioxide-based nano composite photocatalyst. The doping amount of the rare earth in the titanium dioxide-based nano composite photocatalyst accounts for 0.2-2.0 mol%, and the doping amount of the silicon accounts for 5.0-20 mol%. According to the invention, by doping other components such as rare earth, silicon oxide and the like into the nano titanium dioxide crystal, on one hand, the specific surface area of the composite photocatalyst is obviously improved, and on the other hand, the light absorption spectrum of the photocatalyst is expanded to a visible light region, so that the performance of removing VOCs such as formaldehyde and the like is greatly improved.
Yulin and the like successfully prepare the ternary composite photocatalyst consisting of BiOBr, Reduced Graphene Oxide (RGO) and diatomite by using a solvothermal method, characterize the catalyst by using methods such as XRD, SEM, XPS, UV-Vis, BET, ESR and the like, and research the performance and catalytic mechanism of the catalyst for degrading formaldehyde gas under visible light. The result shows that when the mass ratio of the diatomite to the BiOBr is 1.5, the prepared composite photocatalyst has the highest photocatalytic degradation efficiency on formaldehyde gas, the photocatalytic degradation efficiency can reach 89.6% within 3 hours, and the most suitable air relative humidity for application is 45%. After 4 cycles of repeated use, the catalytic performance of the composite photocatalyst is attenuated little. The main active species of the composite photocatalyst for degrading formaldehyde gas are hydroxyl radicals and photo-generated holes, and the high catalytic performance of the composite photocatalyst is mainly benefited by that the diatomite adsorbs and enriches low-concentration formaldehyde gas and RGO increases the separation efficiency of photo-generated carriers.
Although there have been many studies on formaldehyde purification and certain results have been obtained, the formaldehyde purification agent needs to be treated for a long time or the treatment efficiency is not high, so that the development of a new formaldehyde purification agent is still needed to solve the problem.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the prior art and provides a green and odorless formaldehyde purifying agent and a preparation method thereof. The preparation method comprises the following steps: (1) dissolving bismuth salt, samarium salt, ytterbium salt and ferric salt in a hydrochloric acid solution to obtain a mixed solution, then adding diatomite into the mixed solution, and uniformly stirring; then dropwise adding an alkali solution to adjust the pH value to 9-11; then transferring the mixture into a hydrothermal reaction kettle for hydrothermal reaction, naturally cooling the mixture to room temperature, filtering, washing and drying the mixture to obtain a product A; (2) dissolving a molybdenum source, an iron salt, a copper salt and a sulfur source in deionized water to form a solution, stirring, adding the product A prepared in the step (1) into the solution, continuing stirring, transferring the obtained solution into a reaction kettle for reaction, cooling to room temperature, filtering, washing and drying to obtain the formaldehyde purifying agent. The formaldehyde purifying agent prepared by the invention has excellent adsorption capacity and removal capacity on formaldehyde, and has excellent application prospect.
The invention aims to provide a preparation method of a green odorless formaldehyde purifying agent.
The invention also aims to provide a green and odorless formaldehyde purifying agent.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a green odorless formaldehyde purifying agent comprises the following steps:
(1) dissolving bismuth salt, samarium salt, ytterbium salt and ferric salt in a hydrochloric acid solution to obtain a mixed solution, then adding diatomite into the mixed solution, and uniformly stirring; then dropwise adding an alkali solution to adjust the pH value to 9-11; then transferring the mixture into a hydrothermal reaction kettle for hydrothermal reaction, naturally cooling the mixture to room temperature, filtering, washing and drying the mixture to obtain a product A;
(2) dissolving a molybdenum source, an iron salt, a copper salt and a sulfur source in deionized water to form a solution, stirring, adding the product A prepared in the step (1) into the solution, continuing stirring, transferring the obtained solution into a reaction kettle for reaction, cooling to room temperature, filtering, washing and drying to obtain the formaldehyde purifying agent.
Preferably, in the step (1), the bismuth salt is at least one of bismuth nitrate, bismuth acetate or bismuth chloride; the samarium salt is at least one of samarium nitrate, samarium acetate or samarium chloride; the ytterbium salt is at least one of ytterbium nitrate, ytterbium acetate or ytterbium chloride; the ferric salt is at least one of ferric nitrate, ferric acetate or ferric chloride.
Preferably, in the step (1), the concentration of the hydrochloric acid is 0.2-0.6 mol/L; the molar ratio of the bismuth salt to the samarium salt to the ytterbium salt to the iron salt is 0.93-0.97: 0.01 to 0.03; 0.02-0.04: 1.
Preferably, in step (1), the ratio of the iron salt to the diatomaceous earth is 1 mmol: 0.5-1.5 g; the particle size of the diatomite is 0.2-0.5 mu m; the alkali solution is at least one of a sodium hydroxide solution, a potassium hydroxide solution and ammonia water; the concentration of the alkali is 1-3 mol/L.
Preferably, in step (1), the hydrothermal conditions are: carrying out hydrothermal reaction at 190 ℃ and 230 ℃ for 12-20 h; the drying is carried out at the temperature of 90-110 ℃ for 12-18 h.
Preferably, in the step (2), the molybdenum source is sodium molybdate, and the iron salt is at least one of ferric nitrate, ferric acetate or ferric chloride; the copper salt is at least one of copper nitrate, copper acetate or copper chloride; the sulfur source is thiourea or thioacetamide.
Preferably, in the step (2), the stirring time is 20-40 min; and the continuous stirring is carried out for 20-40 min.
Preferably, in the step (2), the molar ratio of the molybdenum source, the ferric salt, the copper salt and the sulfur source is 1: 0.02-0.04: 0.01-0.03: 2-4, the ratio of the product A to the molybdenum source is 1 g: 1 to 3 mmol.
Preferably, in the step (2), the reaction is carried out for 16-28 h at 220-260 ℃; the drying is carried out at the temperature of 90-120 ℃ for 10-20 h.
The formaldehyde purifying agent is prepared by the preparation method of the green odorless formaldehyde purifying agent.
The invention has the following beneficial effects:
(1) by adding the diatomite in the preparation process, the stability of the catalyst can be improved, and low-concentration gaseous formaldehyde can be adsorbed and enriched, so that the purification treatment of the formaldehyde is promoted, and the purification treatment efficiency of the formaldehyde is improved;
(2) co-modified BiFeO by samarium and ytterbium 3 The absorption efficiency of bismuth ferrite on sunlight is promoted, the effective separation of photoproduction electrons and holes is improved, and the purification capacity on formaldehyde is further improved;
(3) molybdenum sulfide is modified by iron and copper together, so that the effective utilization of the molybdenum sulfide to sunlight is promoted, the effective separation of photoproduction electrons and holes is improved, and the formaldehyde purification capacity is further improved;
(4) by modified BiFeO 3 And the modified molybdenum sulfide forms a heterojunction structure, so that the formaldehyde purifying agent is further improved in formaldehyde purifying capacity.
(5) The preparation method is simple, the preparation conditions are mild, and the product performance is excellent, so that the formaldehyde purification material is an ideal material for formaldehyde purification.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A preparation method of a green odorless formaldehyde purifying agent comprises the following steps:
(1) dissolving 9.5mmol of bismuth nitrate, 0.2mmol of samarium nitrate, 0.3mmol of ytterbium nitrate and 10mmol of ferric nitrate in 50mL of 0.4mol/L hydrochloric acid solution to obtain a mixed solution, adding 10g of diatomite (the particle size is 0.4 mu m) into the mixed solution, and uniformly stirring; then dropwise adding 2mol/L potassium hydroxide solution to adjust the pH value to 10; then transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 16h at 210 ℃, then naturally cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain a product A;
(2) dissolving 10mmol of sodium molybdate, 0.3mmol of ferric nitrate, 0.2mmol of copper nitrate and 30mmol of thioacetamide in 50mL of deionized water to form a solution, stirring for 30min, then adding 5g of the product A prepared in the step (1) into the solution, continuing stirring for 30min, then transferring the obtained solution into a reaction kettle, reacting for 22h at 240 ℃, cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain the formaldehyde purifying agent.
Example 2
A preparation method of a green odorless formaldehyde purifying agent comprises the following steps:
(1) dissolving 9.5mmol of bismuth acetate, 0.1mmol of samarium acetate, 0.4mmol of ytterbium chloride and 10mmol of ferric chloride in 50mL of 0.6mol/L hydrochloric acid solution to obtain a mixed solution, adding 15g of diatomite (with the particle size of 0.5 mu m) into the mixed solution, and uniformly stirring; the ratio of the iron salt to the diatomite is 1 mmol: 0.5-1.5 g; then dropwise adding 3mol/L sodium hydroxide solution to adjust the pH value to 11; then transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 12h at 230 ℃, then naturally cooling to room temperature, filtering, washing, and drying for 12h at 110 ℃ to obtain a product A;
(2) dissolving 10mmol of sodium molybdate, 0.4mmol of ferric chloride, 0.1mmol of copper acetate and 40mmol of thiourea in 50mL of deionized water to form a solution, stirring for 40min, then adding 10g of the product A prepared in the step (1) into the solution, continuing stirring for 40min, then transferring the obtained solution into a reaction kettle, reacting for 16h at 260 ℃, cooling to room temperature, filtering, washing, and drying at 120 ℃ for 10h to obtain the formaldehyde purifying agent.
Example 3
A preparation method of a green odorless formaldehyde purifying agent comprises the following steps:
(1) dissolving 9.5mmol of bismuth chloride, 0.3mmol of samarium acetate, 0.2mmol of ytterbium chloride and 10mmol of ferric acetate in 50mL of 0.2mol/L hydrochloric acid solution to obtain a mixed solution, adding 5g of diatomite (with the particle size of 0.2 mu m) into the mixed solution, and uniformly stirring; then dropwise adding 1mol/L ammonia water solution to adjust the pH value to 9; then transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20h at 190 ℃, then naturally cooling to room temperature, filtering, washing, and drying for 18h at 90 ℃ to obtain a product A;
(2) dissolving 10mmol of sodium molybdate, 0.2mmol of iron acetate, 0.3mmol of copper chloride and 20mmol of thioacetamide in 50mL of deionized water to form a solution, stirring for 20min, then adding 3.33g of the product A prepared in the step (1) into the solution, continuing stirring for 20min, then transferring the obtained solution into a reaction kettle, reacting for 28h at 220 ℃, cooling to room temperature, filtering, washing, and drying for 20h at 90 ℃ to obtain the formaldehyde purifying agent.
Comparative example 1
A preparation method of a green odorless formaldehyde purifying agent comprises the following steps:
(1) dissolving 9.5mmol of bismuth nitrate, 0.2mmol of samarium nitrate, 0.3mmol of ytterbium nitrate and 10mmol of ferric nitrate in 50mL of 0.4mol/L hydrochloric acid solution to obtain a mixed solution; then dropwise adding 2mol/L potassium hydroxide solution to adjust the pH value to 10; then transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 16h at 210 ℃, then naturally cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain a product A;
(2) dissolving 10mmol of sodium molybdate, 0.3mmol of ferric nitrate, 0.2mmol of copper nitrate and 30mmol of thioacetamide in 50mL of deionized water to form a solution, stirring for 30min, then adding 5g of the product A prepared in the step (1) into the solution, continuing stirring for 30min, then transferring the obtained solution into a reaction kettle, reacting for 22h at 240 ℃, cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain the formaldehyde purifying agent.
Comparative example 2
A preparation method of a green odorless formaldehyde purifying agent comprises the following steps:
(1) dissolving 9.5mmol of bismuth nitrate, 0.5mmol of samarium nitrate and 10mmol of ferric nitrate in 50ml of 0.4mol/L hydrochloric acid solution to obtain a mixed solution, adding 10g of diatomite (with the particle size of 0.4 mu m) into the mixed solution, and uniformly stirring; then dropwise adding 2mol/L potassium hydroxide solution to adjust the pH value to 10; then transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 16h at 210 ℃, then naturally cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain a product A;
(2) dissolving 10mmol of sodium molybdate, 0.3mmol of ferric nitrate, 0.2mmol of copper nitrate and 30mmol of thioacetamide in 50mL of deionized water to form a solution, stirring for 30min, then adding 5g of the product A prepared in the step (1) into the solution, continuing stirring for 30min, then transferring the obtained solution into a reaction kettle, reacting for 22h at 240 ℃, cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain the formaldehyde purifying agent.
Comparative example 3
A preparation method of a green odorless formaldehyde purifying agent comprises the following steps:
(1) dissolving 9.5mmol of bismuth nitrate, 0.5mmol of ytterbium nitrate and 10mmol of ferric nitrate in 50mL of 0.4mol/L hydrochloric acid solution to obtain a mixed solution, adding 10g of diatomite (with the particle size of 0.4 mu m) into the mixed solution, and uniformly stirring; then dropwise adding 2mol/L potassium hydroxide solution to adjust the pH value to 10; then transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 16h at 210 ℃, then naturally cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain a product A;
(2) dissolving 10mmol of sodium molybdate, 0.3mmol of ferric nitrate, 0.2mmol of copper nitrate and 30mmol of thioacetamide in 50mL of deionized water to form a solution, stirring for 30min, then adding 5g of the product A prepared in the step (1) into the solution, continuing stirring for 30min, then transferring the obtained solution into a reaction kettle, reacting for 22h at 240 ℃, cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain the formaldehyde purifying agent.
Comparative example 4
A preparation method of a green odorless formaldehyde purifying agent comprises the following steps:
(1) dissolving 9.5mmol of bismuth nitrate, 0.2mmol of samarium nitrate, 0.3mmol of ytterbium nitrate and 10mmol of ferric nitrate in 50mL of 0.4mol/L hydrochloric acid solution to obtain a mixed solution, adding 10g of diatomite (the particle size is 0.4 mu m) into the mixed solution, and uniformly stirring; then dropwise adding a potassium hydroxide solution with the concentration of 2mol/L to adjust the pH value to 10; then transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 16h at 210 ℃, then naturally cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain a product A;
(2) dissolving 10mmol of sodium molybdate, 0.5mmol of ferric nitrate and 30mmol of thioacetamide in 50mL of deionized water to form a solution, stirring for 30min, then adding 5g of the product A prepared in the step (1) into the solution, continuing stirring for 30min, then transferring the obtained solution into a reaction kettle, reacting for 22h at 240 ℃, cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain the formaldehyde purifying agent.
Comparative example 5
A preparation method of a green odorless formaldehyde purifying agent comprises the following steps:
(1) dissolving 9.5mmol of bismuth nitrate, 0.2mmol of samarium nitrate, 0.3mmol of ytterbium nitrate and 10mmol of ferric nitrate in 50mL of 0.4mol/L hydrochloric acid solution to obtain a mixed solution, adding 10g of diatomite (the particle size is 0.4 mu m) into the mixed solution, and uniformly stirring; then dropwise adding 2mol/L potassium hydroxide solution to adjust the pH value to 10; then transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 16h at 210 ℃, then naturally cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain a product A;
(2) dissolving 10mmol of sodium molybdate, 0.5mmol of copper nitrate and 30mmol of thioacetamide in 50mL of deionized water to form a solution, stirring for 30min, then adding 5g of the product A prepared in the step (1) into the solution, continuing stirring for 30min, then transferring the obtained solution into a reaction kettle, reacting for 22h at 240 ℃, cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain the formaldehyde purifying agent.
Comparative example 6
A preparation method of a green odorless formaldehyde purifying agent comprises the following steps:
dissolving 9.5mmol of bismuth nitrate, 0.2mmol of samarium nitrate, 0.3mmol of ytterbium nitrate and 10mmol of ferric nitrate in 50mL of 0.4mol/L hydrochloric acid solution to obtain a mixed solution, adding 10g of diatomite (the particle size is 0.4 mu m) into the mixed solution, and uniformly stirring; then dropwise adding 2mol/L potassium hydroxide solution to adjust the pH value to 10; then transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 16h at 210 ℃, then naturally cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain a product A; namely the formaldehyde purifying agent.
Comparative example 7
A preparation method of a green odorless formaldehyde purifying agent comprises the following steps:
dissolving 10mmol of sodium molybdate, 0.3mmol of ferric nitrate, 0.2mmol of copper nitrate and 30mmol of thioacetamide in 50mL of deionized water to form a solution, stirring for 60min, then transferring the obtained solution into a reaction kettle, reacting for 22h at 240 ℃, cooling to room temperature, filtering, washing, and drying for 16h at 100 ℃ to obtain the formaldehyde purifying agent.
The green odorless formaldehyde purifiers prepared in examples 1-3 and comparative examples 1-7 are used in the experiment of degrading formaldehyde by photocatalysis, and the specific experimental steps are as follows:
the photocatalytic degradation performance of formaldehyde was evaluated by using a continuous flow reactor under visible light irradiation at room temperature. First 0.2g of green odorless formaldehyde scavenger was weighed out and coated in the middle of a 4cm x 4cm square plate and placed in the center of the reactor. Adjusting the ratio of formaldehyde gas to air flow to obtain a concentration of 0.8mg/m 3 The flow rate of the formaldehyde gas is controlled to be 1.0L/min. A500W xenon lamp (equipped with a 420nm cut-off filter to shield ultraviolet radiation) was placed vertically on the reactor. Prior to irradiation, the sample coated square plates were kept in the dark for 200min to reach the adsorption-desorption equilibrium. And after the adsorption is finished, switching on a light source. The concentration of residual formaldehyde at 30min and 1h was monitored by a formaldehyde gas analyzer, and the specific test results are shown in table 1.
TABLE 1
| Purification ratio (%) of Formaldehyde at 30min | Purification ratio of Formaldehyde at 1h (%) | |
| Example 1 | 76.2 | 95.3 |
| Example 2 | 75.2 | 93.5 |
| Example 3 | 75.6 | 94.1 |
| Comparative example 1 | 57.7 | 75.5 |
| Comparative example 2 | 73.2 | 91.1 |
| Comparative example 3 | 74.6 | 92.7 |
| Comparative example 4 | 74.1 | 92.1 |
| Comparative example 5 | 74.9 | 93.1 |
| Comparative example 6 | 50.7 | 68.4 |
| Comparative example 7 | 44.7 | 62.3 |
As can be seen from the table 1, the green odorless formaldehyde purifying agent prepared by the invention has excellent purifying capacity of formaldehyde by utilizing the interaction among the components, and the highest purifying rate reaches 95.3%, so that the green odorless formaldehyde purifying agent has excellent application prospect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a green odor-free formaldehyde purifying agent is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) dissolving bismuth salt, samarium salt, ytterbium salt and ferric salt in a hydrochloric acid solution to obtain a mixed solution, then adding diatomite into the mixed solution, and uniformly stirring; then dropwise adding an alkali solution to adjust the pH value to 9-11; then transferring the mixture into a hydrothermal reaction kettle for hydrothermal reaction, naturally cooling the mixture to room temperature, filtering, washing and drying the mixture to obtain a product A;
(2) dissolving a molybdenum source, an iron salt, a copper salt and a sulfur source in deionized water to form a solution, stirring, adding the product A prepared in the step (1) into the solution, continuing stirring, transferring the obtained solution into a reaction kettle for reaction, cooling to room temperature, filtering, washing and drying to obtain the formaldehyde purifying agent.
2. The method for preparing the green odorless formaldehyde scavenger according to claim 1, which is characterized in that: in the step (1), the bismuth salt is at least one of bismuth nitrate, bismuth acetate or bismuth chloride; the samarium salt is at least one of samarium nitrate, samarium acetate or samarium chloride; the ytterbium salt is at least one of ytterbium nitrate, ytterbium acetate or ytterbium chloride; the ferric salt is at least one of ferric nitrate, ferric acetate or ferric chloride.
3. The method for preparing the green odorless formaldehyde scavenger according to claim 1, which is characterized in that: in the step (1), the concentration of the hydrochloric acid is 0.2-0.6 mol/L; the molar ratio of the bismuth salt to the samarium salt to the ytterbium salt to the iron salt is 0.93-0.97: 0.01 to 0.03; 0.02-0.04: 1.
4. The method for preparing the green odorless formaldehyde scavenger according to claim 1, which is characterized in that: in step (1), the ratio of the iron salt to diatomaceous earth is 1 mmol: 0.5-1.5 g; the particle size of the diatomite is 0.2-0.5 mu m; the alkali solution is at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water; the concentration of the alkali is 1-3 mol/L.
5. The method for preparing the green odorless formaldehyde scavenger according to claim 1, which is characterized in that: in the step (1), the hydrothermal conditions are as follows: carrying out hydrothermal reaction at 190 ℃ and 230 ℃ for 12-20 h; the drying is carried out at the temperature of 90-110 ℃ for 12-18 h.
6. The preparation method of the green odorless formaldehyde scavenger according to claim 1, which is characterized in that: in the step (2), the molybdenum source is sodium molybdate, and the ferric salt is at least one of ferric nitrate, ferric acetate or ferric chloride; the copper salt is at least one of copper nitrate, copper acetate or copper chloride; the sulfur source is thiourea or thioacetamide.
7. The method for preparing the green odorless formaldehyde scavenger according to claim 1, which is characterized in that: in the step (2), the stirring time is 20-40 min; and the continuous stirring is carried out for 20-40 min.
8. The method for preparing the green odorless formaldehyde scavenger according to claim 1, which is characterized in that: in the step (2), the molar ratio of the molybdenum source, the ferric salt, the copper salt and the sulfur source is 1: 0.02-0.04: 0.01-0.03: 2-4, the ratio of the product A to the molybdenum source is 1 g: 1 to 3 mmol.
9. The preparation method of the green odorless formaldehyde scavenger according to claim 1, which is characterized in that: in the step (2), the reaction is carried out for 16-28 h at 220-260 ℃; the drying is carried out at the temperature of 90-120 ℃ for 10-20 h.
10. A formaldehyde scavenger prepared by the method for preparing a green odorless formaldehyde scavenger according to any one of claims 1 to 9.
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