CN111097422B - Catalyst for removing formaldehyde and preparation method and application thereof - Google Patents
Catalyst for removing formaldehyde and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a formaldehyde-removing catalyst and a preparation method and application thereof. The formaldehyde removing catalyst is prepared by the following preparation method: 1) Dissolving two transition metal salts in water to prepare a precursor solution; wherein the two transition metal salts are selected from any two metal salts of nickel, cobalt, iron, molybdenum, manganese, magnesium and aluminum; 2) Adding an organic amine solution into the precursor solution, and mixing and stirring to obtain a mixed solution; 3) And carrying out hydrothermal reaction on the mixed solution to obtain the double metal hydroxide catalyst. The catalyst prepared by the invention contains abundant surface hydroxyl groups, can promote the adsorption and oxidation of indoor formaldehyde, can completely convert the indoor formaldehyde into carbon dioxide and water at normal temperature and normal pressure without adding noble metals, and has a removal rate of over 90 percent. The catalyst has the advantages of wide raw material source, simple synthesis method, low manufacturing cost and the like, and is easy for industrial production.
Description
Technical Field
The invention relates to the technical field of air purification, in particular to a formaldehyde-removing catalyst and a preparation method and application thereof.
Background
Indoor air pollution seriously harms human life health, and formaldehyde, a common indoor air pollutant, has been listed as a carcinogen by the world health organization. The limit of the concentration of formaldehyde in indoor air specified in indoor air quality Standard of China is 0.10mg/m 3 . The formaldehyde pollution in the room is treated urgently because the formaldehyde pollution is in a low-dosage formaldehyde environment for a long time and is easy to cause diseases such as respiratory tract damage, pulmonary edema, leukemia and the like. At present, the indoor formaldehyde purification mainly depends on natural ventilation, active porous carbon adsorption and nano TiO 2 Photocatalysis, catalytic oxidation with catalyst, etc. The catalytic oxidation technology can completely oxidize the formaldehyde into CO which is harmless to human bodies under the catalytic action of the catalyst 2 And H 2 O, is the most potential application technology.
The research and development difficulty of the catalytic oxidation technology is mainly used for preparing the catalyst with low temperature, high efficiency, low cost and good stability. The catalyst for efficiently catalyzing and oxidizing formaldehyde at room temperature is mainly a noble metal-loaded catalyst, and common carriers mainly comprise active carbon and SiO 2 And metal oxides, however, the catalysts have high precious metal content, which results in high raw material cost and is not favorable for practical industrial application. Many studies have shown that abundant surface hydroxyl groups are beneficial for adsorption of formaldehyde gas and oxygenAnd (4) melting. For example, CN105013491A mentions an alkali modified NiCo 2 O 4 The catalyst has a large amount of hydroxyl groups on the surface, and can catalyze and oxidize formaldehyde at room temperature, but the preparation process of the catalyst is complex, high-temperature calcination is needed, and the cost is high; and mainly aims at high-concentration formaldehyde (50 ppm), which is not practical.
Layered Double Hydroxides (LDHs) are commonly called hydrotalcite, are anionic clay materials, contain rich hydroxyl groups, and are often applied to the fields of lithium ion batteries, supercapacitors, catalysis and the like. At present, pt/NiFe-LDH catalysts are reported to be used for formaldehyde catalytic oxidation and can completely decompose formaldehyde at the temperature of 60 ℃, but the defect of overhigh cost in practical application due to the introduction of noble metals still exists. LDHs not only have abundant hydroxyl groups, but also have excellent redox activity between double metals, and are also researched as supercapacitor materials and photocatalysts in recent years. However, the LDHs is not reported in the field of directly using the LDHs for room-temperature catalytic oxidation of indoor formaldehyde.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a double metal hydroxide formaldehyde-removing catalyst which has high catalytic activity at room temperature, simple preparation and low cost, and also provides a preparation method and application of the formaldehyde-removing catalyst.
The invention concept of the invention is as follows: organic amine is used as a precipitator, and the organic amine and two transition metal salt solutions are subjected to hydrothermal reaction to prepare the double-metal hydroxide catalyst which is suitable for removing formaldehyde in indoor air.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a formaldehyde removal catalyst, which comprises the following steps:
1) Dissolving two transition metal salts in water to prepare a precursor solution;
2) Adding an organic amine solution into the precursor solution, and mixing and stirring to obtain a mixed solution;
3) Carrying out hydrothermal reaction on the mixed solution to obtain a double metal hydroxide catalyst;
in step 1) of the preparation method, the two transition metal salts are metal salts of any two of nickel, cobalt, iron, molybdenum, manganese, magnesium and aluminum.
Preferably, in step 1) of the preparation method, the two transition metal salts may be respectively selected from any one of nickel salts and cobalt salts, nickel salts and iron salts, cobalt salts and manganese salts, nickel salts and molybdenum salts, cobalt salts and molybdenum salts, nickel salts and aluminum salts, and cobalt salts and iron salts.
Preferably, in the transition metal salt in step 1), the nickel salt is selected from at least one of nickel nitrate, nickel acetate, nickel sulfate and nickel chloride; the cobalt salt is at least one selected from cobalt nitrate, cobalt acetate, cobalt sulfate and cobalt chloride; the ferric salt is at least one selected from ferric nitrate, ferric acetate, ferric sulfate and ferric chloride; the molybdenum salt is at least one selected from molybdenum nitrate, molybdenum acetate, molybdenum sulfate, molybdenum chloride and ammonium molybdate; the manganese salt is selected from at least one of manganese nitrate, manganese acetate, manganese sulfate and manganese chloride; the magnesium salt is selected from at least one of magnesium nitrate, magnesium acetate, magnesium sulfate and magnesium chloride; the aluminum salt is at least one selected from aluminum nitrate, aluminum acetate, aluminum sulfate and aluminum chloride; further preferably, the two transition metal salts are selected from any one of nickel nitrate and cobalt nitrate, nickel acetate and iron acetate, cobalt sulfate and manganese sulfate, nickel nitrate and molybdenum nitrate, cobalt chloride and ammonium molybdate, nickel nitrate and aluminum nitrate, cobalt nitrate and iron nitrate.
Preferably, in step 1) of this preparation method, the molar ratio between the two transition metal salts is 1: (0.5-2).
Preferably, in step 1) of the preparation method, the total concentration of the transition metal salt in the precursor solution is 0.05 mol/L-0.1 mol/L; further preferably, the total concentration of the transition metal salt in the precursor solution is 0.07mol/L to 0.08mol/L. The total concentration of transition metal salts refers to the sum of the concentrations of the two transition metal salts.
Preferably, in step 2) of the preparation method, the molar ratio of the transition metal salt to the organic amine in the precursor solution is 1: (1.5 to 12); further preferably, the molar ratio of the transition metal salt to the organic amine in the precursor solution is 1: (2-8).
Preferably, in step 2) of the preparation method, the organic amine concentration of the organic amine solution is 0.2mol/L to 1.5mol/L; more preferably, the organic amine concentration of the organic amine solution is 0.3mol/L to 1.2mol/L.
Preferably, in the organic amine solution in step 2) of the preparation method, the organic amine is at least one selected from urea, ammonia water, diethylamine, oleylamine, hexadecylamine, hexylamine, and hexamethylenetetramine; more preferably, the organic amine is at least one selected from the group consisting of urea, aqueous ammonia, diethylamine, oleylamine, and hexamethylenetetramine. In the preparation method of the catalyst, organic amine is used as a precipitator, the change range of the pH value is small, and hexagonal nanosheets with regular shapes can be obtained.
Preferably, in the organic amine solution in step 2) of the preparation method, the solvent is at least one selected from water, methanol, ethanol, ethylene glycol and isopropanol; further preferably, the solvent is at least one selected from the group consisting of water, ethanol, and ethylene glycol.
Preferably, in step 2) of the preparation method, the organic amine solution is added to the precursor solution by dropwise addition.
Preferably, in step 2) of the preparation method, the mixing and stirring are carried out in a magnetic stirrer; the stirring speed is 300r/min to 600r/min, and the stirring time is 0.5h to 2h.
Preferably, in step 3) of the preparation method, the temperature of the hydrothermal reaction is 120-180 ℃, and the time of the hydrothermal reaction is 10-18 h.
Preferably, in step 3) of the preparation method, the hydrothermal reaction is carried out in a polytetrafluoroethylene reaction kettle in a sealing way.
Preferably, in step 3) of the preparation method, the hydrothermal reaction further comprises the steps of washing, filtering and drying the product. Wherein, the washing is preferably to wash the product with absolute ethyl alcohol for 2 to 3 times and then wash with water for 2 to 3 times. The drying temperature is preferably 80-110 ℃, and the drying time is preferably 8-24 h.
Preferably, in this preparation method, the water used is deionized water.
The invention provides a formaldehyde-removing catalyst, which is prepared by the preparation method. The catalyst is a layered double hydroxide having a hexagonal morphology.
The invention also provides the application of the formaldehyde removal catalyst.
An application of the catalyst prepared by the preparation method in removing formaldehyde in indoor air.
The catalyst of the invention can be applied to removing low-concentration formaldehyde in air. Preferably, in application, the initial concentration of formaldehyde in the air is less than or equal to 1.5mg/m 3 。
Further, the formaldehyde in the indoor air can be adsorbed by using the catalyst, and the formaldehyde can be catalytically oxidized into carbon dioxide and water. The treatment can be carried out at room temperature without adding noble metals.
The beneficial effects of the invention are:
the catalyst prepared by the invention contains abundant surface hydroxyl, can promote the adsorption and oxidation of indoor formaldehyde, can completely convert the indoor formaldehyde into carbon dioxide and water at normal temperature and normal pressure without adding noble metals, and has a removal rate of 90% or more. The catalyst has the advantages of wide raw material source, simple synthesis method, low manufacturing cost and the like, and is easy for industrial production.
Specifically, compared with the prior art, the invention has the following advantages:
1) According to the invention, the LDHs formaldehyde catalyst with a hexagonal shape is obtained by reacting a solution containing two transition metal salts with an organic amine precipitator in a hydrothermal kettle, and the LDHs laminate has abundant surface hydroxyl groups, so that the adsorption and oxidation of formaldehyde are facilitated. In addition, the redox cycling reaction between the transition metals accelerates the absorption and transfer of oxygen in the air, and provides more active sites for formaldehyde oxidation.
2) The catalyst prepared by the method has high activity, does not need to add noble metals, has very obvious formaldehyde purification effect at room temperature, and greatly reduces the production cost of the catalyst.
Drawings
FIG. 1 is an XRD pattern of NiCo-LDHs catalyst of example 1 except that formaldehyde;
FIG. 2 is a SEM photograph of the formaldehyde removing catalyst NiCo-LDHs of example 1;
FIG. 3 is an XPS plot of NiCo-LDHs as formaldehyde-removing catalysts in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The raw materials, reagents or apparatuses used in the examples and comparative examples were all available from conventional commercial sources unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
Example 1
A NiCo-LDHs catalyst is prepared by the following specific steps:
dissolving 1mmol of nickel nitrate and 2mmol of cobalt nitrate in 40mL of deionized water to obtain a precursor solution; preparing 20mL of ethanol solution containing 24mmol of oleylamine, dropwise adding the ethanol solution into the precursor solution, and stirring the solution for 0.5h at 600r/min by using a magnetic stirrer after the dropwise adding of the precipitator is finished; transferring the stirred solution into a polytetrafluoroethylene high-pressure kettle, sealing, carrying out hydrothermal reaction, adjusting the reaction temperature to 180 ℃, and fully reacting for 12 hours. And after the reaction is finished, cooling to room temperature, washing the product for 3 times by using absolute ethyl alcohol and deionized water in sequence, filtering, and drying at 90 ℃ for 12 hours to obtain the NiCo-LDHs catalyst.
FIG. 1 is the XRD pattern of NiCo-LDHs catalyst of example 1 except formaldehyde. As can be seen from FIG. 1, the NiCo-LDHs catalyst prepared in this example is composed of beta-Ni (OH) 2 And beta-Co (OH) 2 A solid solution is formed.
FIG. 2 is an SEM photograph of the formaldehyde removing catalyst NiCo-LDHs of example 1. As can be seen from FIG. 2, the NiCo-LDHs catalyst prepared by the method has a layered structure and a hexagonal special morphology.
FIG. 3 is an XPS plot of NiCo-LDHs as formaldehyde-removing catalysts in example 1. As can be seen from FIG. 3, hydroxyl groups are present in the NiCo-LDHs catalyst prepared in this example.
Example 2
A NiFe-LDHs catalyst is prepared by the following specific steps:
dissolving 1.5mmol of nickel acetate and 1.5mmol of iron acetate in 40mL of deionized water to obtain a precursor solution; preparing 20mL of ethanol solution containing 15mmol of oleylamine, dropwise adding the ethanol solution into the precursor solution, and stirring the mixture for 1h at 500r/min by using a magnetic stirrer after the dropwise adding of the precipitator is finished; transferring the stirred solution into a polytetrafluoroethylene high-pressure kettle, sealing, carrying out hydrothermal reaction, adjusting the reaction temperature to 160 ℃, and fully reacting for 14 hours. And after the reaction is finished, cooling to room temperature, washing the product for 3 times by using absolute ethyl alcohol and deionized water in sequence, filtering, and drying at 110 ℃ for 8 hours to obtain the NiFe-LDHs catalyst.
Example 3
A CoMn-LDHs catalyst is prepared by the following specific steps:
dissolving 2mmol of cobalt sulfate and 1mmol of manganese sulfate in 40mL of deionized water to obtain a precursor solution; preparing 20mL of ethanol solution containing 12mmol of oleylamine, dropwise adding the ethanol solution into the precursor solution, and stirring for 2 hours at 300r/min by using a magnetic stirrer after the dropwise adding of the precipitator is finished; transferring the stirred solution into a polytetrafluoroethylene high-pressure kettle, sealing, carrying out hydrothermal reaction, adjusting the reaction temperature to 120 ℃, and fully reacting for 18h. And after the reaction is finished, cooling to room temperature, washing the product for 3 times by using absolute ethyl alcohol and deionized water in sequence, filtering, and drying at 100 ℃ for 10 hours to obtain the CoMn-LDHs catalyst.
Example 4
A NiMo-LDHs catalyst is prepared by the following specific steps:
dissolving 1mmol of nickel nitrate and 2mmol of molybdenum nitrate in 40mL of deionized water to obtain a precursor solution; preparing 20mL of deionized water solution containing 6mmol of urea, dropwise adding the solution into the precursor solution, and stirring for 0.5h at 600r/min by using a magnetic stirrer after the dropwise adding of the precipitator is finished; transferring the stirred solution into a polytetrafluoroethylene high-pressure kettle, sealing, carrying out hydrothermal reaction, adjusting the reaction temperature to 180 ℃, and fully reacting for 10 hours. And after the reaction is finished, cooling to room temperature, washing the product for 3 times by using absolute ethyl alcohol and deionized water in sequence, filtering, and drying at 80 ℃ for 12 hours to obtain the NiMo-LDHs catalyst.
Example 5
A CoMo-LDHs catalyst is prepared by the following specific steps:
dissolving 1mmol of cobalt chloride and 2mmol of ammonium molybdate with 40mL of deionized water to obtain a precursor solution; preparing 20mL of glycol solution containing 6mmol of hexamethylenetetramine, dropwise adding the glycol solution into the precursor solution, and stirring for 0.5h at 600r/min by using a magnetic stirrer after the dropwise adding of the precipitant is finished; transferring the stirred solution into a polytetrafluoroethylene high-pressure kettle, sealing, carrying out hydrothermal reaction, adjusting the reaction temperature to 180 ℃, and fully reacting for 12 hours. And after the reaction is finished, cooling to room temperature, washing the product for 3 times by using absolute ethyl alcohol and deionized water in sequence, filtering, and drying at 90 ℃ for 12 hours to obtain the CoMo-LDHs catalyst.
Example 6
A NiAl-LDHs catalyst is prepared by the following specific steps:
dissolving 1mmol of nickel nitrate and 2mmol of aluminum nitrate in 40mL of deionized water to obtain a precursor solution; preparing 20mL of deionized water solution containing 6mmol of ammonia water, dropwise adding the deionized water solution into the precursor solution, and stirring for 0.5h at 600r/min by using a magnetic stirrer after the dropwise adding of the precipitator is finished; transferring the stirred solution into a polytetrafluoroethylene high-pressure kettle, sealing, carrying out hydrothermal reaction, adjusting the reaction temperature to 180 ℃, and fully reacting for 12 hours. And after the reaction is finished, cooling to room temperature, washing the product for 3 times by using absolute ethyl alcohol and deionized water in sequence, filtering, and drying at 90 ℃ for 12 hours to obtain the NiMn-LDHs catalyst.
Example 7
A CoFe-LDHs catalyst is prepared by the following specific steps:
dissolving 1mmol of cobalt nitrate and 2mmol of ferric nitrate in 40mL of deionized water to obtain a precursor solution; preparing 20mL of ethanol solution containing 6mmol of diethylamine, dropwise adding the ethanol solution into the precursor solution, and stirring for 0.5h at 600r/min by using a magnetic stirrer after the dropwise adding of the precipitator is finished; transferring the stirred solution into a polytetrafluoroethylene high-pressure kettle, sealing, carrying out hydrothermal reaction, adjusting the reaction temperature to 180 ℃, and fully reacting for 12 hours. And after the reaction is finished, cooling to room temperature, washing the product for 3 times by using absolute ethyl alcohol and deionized water in sequence, filtering, and drying at 90 ℃ for 12 hours to obtain the CoFe-LDHs catalyst.
Comparative example 1
A Ni-LDHs catalyst is prepared by the following specific steps:
dissolving 3mmol of nickel nitrate in 40mL of deionized water to obtain a precursor solution; preparing 20mL of ethanol solution containing 12mmol of oleylamine, dropwise adding the ethanol solution into the precursor solution, and stirring for 0.5h at 600r/min by using a magnetic stirrer after the dropwise adding of the precipitator is finished; transferring the stirred solution into a polytetrafluoroethylene high-pressure kettle, sealing, carrying out hydrothermal reaction, adjusting the reaction temperature to 180 ℃, and fully reacting for 12 hours. And after the reaction is finished, cooling to room temperature, washing the product for 3 times by using absolute ethyl alcohol and deionized water in sequence, filtering, and drying at 90 ℃ for 12 hours to obtain the Ni-LDHs catalyst.
Comparative example 2
A Co-LDHs catalyst is prepared by the following specific steps:
dissolving 3mmol of cobalt nitrate in 40mL of deionized water to obtain a precursor solution; preparing 20mL of ethanol solution containing 12mmol of oleylamine, dropwise adding the ethanol solution into the precursor solution, and stirring for 0.5h at 600r/min by using a magnetic stirrer after the dropwise adding of the precipitator is finished; transferring the stirred solution into a polytetrafluoroethylene high-pressure kettle, sealing, carrying out hydrothermal reaction, adjusting the reaction temperature to 180 ℃, and fully reacting for 12 hours. And after the reaction is finished, cooling to room temperature, washing the product for 3 times by using absolute ethyl alcohol and deionized water in sequence, filtering, and drying at 90 ℃ for 12 hours to obtain the Co-LDHs catalyst.
Comparative example 3
NiCo 2 O 4 The catalyst is prepared by the following specific steps:
dissolving 1mmol of nickel nitrate and 2mmol of cobalt nitrate in 40mL of deionized water to obtain a precursor solution; preparing 20mL of ethanol solution containing 24mmol of oleylamine, dropwise adding the ethanol solution into the precursor solution, and stirring the solution for 0.5h at 600r/min by using a magnetic stirrer after the dropwise adding of the precipitator is finished; transferring the stirred solution into a polytetrafluoroethylene high-pressure kettle, sealing, carrying out hydrothermal reaction, adjusting the reaction temperature to 180 ℃, and fully reacting for 12 hours. After the reaction is finished, cooling to room temperature, washing the product for 3 times by using absolute ethyl alcohol and deionized water in sequence, filtering, and drying for 12 hours at 90 ℃. Then the dried sample is put into a crucible and put into a muffle furnace to be calcined for 5 hours at 200 ℃,obtaining NiCo 2 O 4 A catalyst.
Catalytic oxidation test of formaldehyde
In order to examine the effect of the catalyst prepared according to the present invention in catalyzing the oxidation of formaldehyde, 0.1g each of the catalyst prepared in examples 1 to 7 and the catalyst prepared in comparative examples 1 to 3 was charged into a continuous flow fixed bed reactor, and formaldehyde in an aqueous formaldehyde solution was bubbled into the reactor charged with the catalyst at room temperature using air at an initial formaldehyde concentration of 0.8mg/m 3 The space velocity is 60000mL g -1 ·h -1 . And measuring the ultraviolet absorbance of the formaldehyde at 630nm by adopting a phenol reagent spectrophotometry, then converting corresponding formaldehyde inlet and outlet concentrations, and calculating the corresponding formaldehyde conversion rate. The test results are shown in Table 1.
TABLE 1 Formaldehyde removal test results
From the test results in table 1, it can be seen that the bimetallic hydroxide catalyst prepared by the present invention has high catalytic activity, and the formaldehyde removal rate at room temperature can reach 90% or more.
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 modifications are intended to be included in the scope of the present invention.
Claims (8)
1. The application of the formaldehyde removal catalyst in removing formaldehyde in indoor air is characterized in that:
the preparation method of the formaldehyde removal catalyst comprises the following steps:
1) Dissolving two transition metal salts in water to prepare a precursor solution;
2) Adding an organic amine solution into the precursor solution, and mixing and stirring to obtain a mixed solution;
3) Carrying out hydrothermal reaction on the mixed solution to obtain a double metal hydroxide catalyst;
in the step 1), the two transition metal salts are respectively selected from any one group of nickel salt and cobalt salt, nickel salt and iron salt, cobalt salt and manganese salt, nickel salt and molybdenum salt, cobalt salt and molybdenum salt, nickel salt and aluminum salt, cobalt salt and iron salt;
in the organic amine solution in the step 2), the organic amine is selected from at least one of urea, ammonia water, diethylamine, oleylamine, hexadecylamine, hexylamine and hexamethylenetetramine.
2. Use according to claim 1, characterized in that: in step 1) of the preparation method, the molar ratio of the former to the latter in the two transition metal salts is 1: (0.5 to 2).
3. Use according to claim 1, characterized in that: in the step 1) of the preparation method, the total concentration of the transition metal salt in the precursor solution is 0.05-0.1 mol/L.
4. Use according to claim 1, characterized in that: in the step 2) of the preparation method, the molar ratio of the transition metal salt of the precursor solution to the organic amine is 1: (1.5 to 12).
5. Use according to claim 1, characterized in that: in the step 2) of the preparation method, the concentration of the organic amine in the organic amine solution is 0.2-1.5 mol/L.
6. Use according to claim 5, characterized in that: in step 2) of the preparation method, the solvent is at least one selected from water, methanol, ethanol, ethylene glycol and isopropanol.
7. Use according to claim 1, characterized in that: in the step 3) of the preparation method, the temperature of the hydrothermal reaction is 120-180 ℃, and the time of the hydrothermal reaction is 10h-18h.
8. Use according to claim 1, characterized in that: in the step 3), the method further comprises the steps of washing, filtering and drying the product after the hydrothermal reaction.
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| CN113000052B (en) * | 2021-02-19 | 2022-02-15 | 厦门大学 | Wet oxidation catalyst and preparation method and application thereof |
| CN114573034B (en) * | 2021-12-31 | 2024-03-22 | 武汉工程大学 | Method for preparing layered iron-aluminum double metal hydroxide from Bayer red mud |
| CN115487826A (en) * | 2022-09-26 | 2022-12-20 | 江苏中江材料技术研究院有限公司 | Silver-doped manganese-cobalt hydrotalcite catalyst, preparation method thereof and method for degrading formaldehyde |
| CN115739113A (en) * | 2022-11-23 | 2023-03-07 | 大气(广东)科技发展有限公司 | Catalyst for catalyzing formaldehyde at room temperature and preparation method thereof |
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