CN115041139A - Amino formaldehyde adsorbent and preparation method thereof - Google Patents
Amino formaldehyde adsorbent and preparation method thereof Download PDFInfo
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
The invention discloses an amino formaldehyde adsorbent and a preparation method thereof, and the preparation process is simple, environment-friendly, safe and low in cost. By loading the amino adsorbate on the base material, the selectivity of the amino to formaldehyde is fully utilized, formaldehyde gas can be rapidly enriched on the surface of the adsorbent and subjected to chemical addition reaction, the aim of thoroughly removing formaldehyde is fulfilled, and secondary pollution can be effectively inhibited. In addition, the specific surface area of the porous substance can be obviously improved through the substrate material modified and pretreated by a specific process, the internal pore channel structure is further modified, microscopic pore formation is realized, the loading capacity of the amino-based adsorbate is further improved, the adsorption effect is greatly optimized, the formaldehyde removal rate in 24 hours is basically stabilized to be more than 95%, and the adsorption capacity can even be as high as more than 70 mg/g. Moreover, the adsorbent still shows excellent formaldehyde adsorption effect in high-temperature environment, humid environment and acid-base environment.
Description
Technical Field
The invention relates to a formaldehyde adsorbent, in particular to an amino formaldehyde adsorbent and a preparation method thereof; belongs to the technical field of air pollution purification.
Background
Formaldehyde is a colorless gas with pungent smell, is known as the first killer of home decoration, has the characteristics of wide pollution range, long duration, great harmfulness and the like, seriously harms human health, has strong stimulation effect on human skin and mucous membrane, can cause selective damage to vision and retina, and can cause neurasthenia symptoms such as memory deterioration, somnolence and the like after being contacted with formaldehyde for a long time. More seriously, formaldehyde can cause severe diseases such as several cancers of human bodies, leukemia of children and the like, so that effective treatment of formaldehyde pollution has attracted great social attention.
In order to solve the problem of volatile pollution of formaldehyde, there are some methods or materials for removing formaldehyde:
(1) by conventional means
By utilizing the characteristic that formaldehyde is soluble in water, the tea water is put into a room and is windowed for ventilation, and the pungent smell is basically eliminated; optionally placing some plants such as scindapsus aureus indoors; this method is only a reduction in the sensory odor, but actually only covers the formaldehyde odor with another odor, and harmful gases are always present in the environment.
(2) Ventilation method
The content of harmful substances in the indoor air can be reduced through the circulation of the indoor air, so that the harm of the substances to human bodies is reduced.
(3) Adsorption process
The method for purifying indoor pollutant which is widely applied for a long time and has the most stable effect is an activated carbon physical adsorption method, and an adsorbed substance firstly contacts the outer surface of the activated carbon and then enters macropores, mesopores and micropores of the activated carbon to achieve the purification effect. But formaldehyde has low molecular weight and strong polarity, is difficult to completely remove by physical adsorption, and can be reversely released even after the adsorption is saturated, so that the purification effect is unsatisfactory.
For the above reasons, it is necessary to develop new formaldehyde adsorption technology and adsorption products to optimize formaldehyde adsorption effect.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a formaldehyde adsorbent which is good in adsorption effect, high in formaldehyde removal rate and large in adsorption capacity, and a preparation method thereof.
In order to achieve the above object, the present invention adopts the following technical solutions:
the invention firstly claims a preparation method of an amino formaldehyde adsorbent, which comprises the following steps:
s1, preparation of an intermediate:
dissolving caprolactam in benzene to prepare a solution 1; adding 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride into a reflux stirring device containing benzene, heating to 35-40 ℃, fully and uniformly mixing, then dropwise adding the solution 1 into the reflux stirring device, and controlling the reaction temperature; after the dropwise adding is finished, heating to 65-80 ℃, refluxing, and continuously reacting for 2-3 h; after the reaction is finished, removing unreacted reactants and solvent by rotary evaporation to obtain an intermediate; in this step, the temperature is raised to remove HCl generated by the reaction, and the reflux prevents evaporation of other substances than HCl.
S2, preparing amino adsorbate:
dissolving the intermediate prepared in the step S1 in benzene, stirring and heating to 30-35 ℃, and slowly introducing excessive ammonia gas for reaction after complete mixing; after the reaction is finished, washing with water to remove entrained impurity NH 4 Br and NH 3 Removing the solvent by rotary evaporation to obtain an amino adsorbate;
the reaction mechanism of the preparation process of the amino adsorbate is as follows:
s3, load: and loading the amino adsorbate on a base material to obtain the target product, namely the amino formaldehyde adsorbent.
Preferably, in the aforementioned step S1, the molar ratio of caprolactam to 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] carbonyl chloride is 1: (0.5-2).
More preferably, in the aforementioned step S1, the molar ratio of 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] carbonyl chloride to benzene in the reflux mixer is 1: (1-3).
More preferably, in the step S1, the reaction temperature is controlled to be 50 to 55 ℃.
Still preferably, in the step S2, the molar ratio of the intermediate to benzene is 1: (2-4) reacting the intermediate with benzene in a ratio of 1: 2, and in view of the solution concentration, it is preferable not to exceed 1: 4..
Still preferably, in the step S3, the specific loading process is as follows: dissolving amino adsorbate in an organic solvent, wherein the solid-liquid ratio (volume ratio) of the amino adsorbate to a matrix material is 1: (0.2-1), stirring and mixing uniformly, and keeping constant temperature for 6-24 hours at the vacuum condition of 60-80 ℃ to obtain the target product. The organic solvent can adopt ethyl acetate or benzene, and the like, so long as the amine adsorbate can be dissolved, and the organic solvent with low pollution is selected as far as possible by combining the environment-friendly principle.
Further preferably, in the step S3, the matrix material is a porous substance, and the porous substance is activated carbon or zeolite.
Still more preferably, the aforementioned porous substance is subjected to the following pretreatment: and (4) keeping the mixture in a vacuum constant-temperature environment at 80-90 ℃ for 4-6 hours.
Still further preferably, the porous substance is further subjected to a modification treatment before the pretreatment: mixing a sodium carbonate solution and an ammonium chloride solution, soaking and boiling the porous substance at 60-80 ℃ for 6-18 h, washing with dilute hydrochloric acid and deionized water in sequence, drying, transferring to a quartz boat, heating to 400-600 ℃, keeping the temperature for 3-5 min, naturally cooling, and then pretreating. The specific surface area of the porous substance can be obviously improved through the modification treatment, the internal pore channel structure of the porous substance is improved, microscopic pore forming is realized, the loading capacity of the amino adsorbate can be improved, and the adsorption effect is further optimized.
The invention also claims an amino formaldehyde adsorbent prepared by the preparation method.
The invention has the advantages that:
(1) the preparation process of the amino formaldehyde adsorbent is simple, environment-friendly, safe, low in cost and free of secondary pollution, and has excellent industrial popularization and application values and prospects.
(2) According to the amino formaldehyde adsorbent prepared by the invention, an amino adsorbate is loaded on a base material, and through the selectivity of amino to formaldehyde, formaldehyde gas can be rapidly enriched on the surface of the adsorbent and subjected to chemical addition reaction, so that the aim of thoroughly removing formaldehyde is fulfilled, and secondary pollution can be effectively inhibited; meanwhile, the matrix material with the porous characteristic can completely adsorb impurities in the air through physical adsorption, so that the adsorption performance is further optimized.
(3) According to the invention, after the substrate material is treated by a specific modification and pretreatment process, the specific surface area of the porous substance as the substrate material can be obviously improved, the internal pore structure is modified, the microscopic pore-forming is realized, the loading capacity of the amine adsorbate is further improved, and the adsorption effect is greatly optimized. Proved by verification, the amino formaldehyde adsorbent prepared by the process has excellent performance, the formaldehyde removal rate is stabilized to be more than 95% in 24 hours, and the adsorption capacity is basically more than 50mg/g and even can be as high as 70.3 mg/g.
(4) The amino formaldehyde adsorbent prepared by the invention has the characteristics of water resistance, acid and alkali resistance, and the melting point is more than 70 ℃, so that the amino formaldehyde adsorbent shows excellent formaldehyde adsorption effect in high-temperature environment, humid environment and acid-alkali environment.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Example 1
The preparation method of the amino formaldehyde adsorbent of the embodiment comprises the following steps:
s1, preparation of an intermediate:
0.2mol (22.6g) of caprolactam was dissolved in benzene to give solution 1; adding 0.2mol of 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride into a reflux stirring device containing 0.2mol of benzene, heating to 40 ℃, fully and uniformly mixing, then dropwise adding the solution 1 into the reflux stirring device, and controlling the reaction temperature to be 50 ℃; after the dropwise addition is finished, heating to 70 ℃, refluxing, and continuously reacting for 2 hours; after the reaction is finished, removing unreacted reactants and solvent by rotary evaporation to obtain an intermediate;
s2, preparing amino adsorbate:
dissolving 0.1mol of the intermediate prepared in the step S1 in 0.2mol of benzene, stirring and heating to 35 ℃, and slowly introducing excessive ammonia gas for reaction after complete mixing; after the reaction is finished, washing the reaction product by water to remove entrained impurity NH 4 Br and NH 3 Removing the solvent by rotary evaporation to obtain an amino adsorbate;
s3, load: and loading the amino adsorbate on a base material to obtain the target product, namely the amino formaldehyde adsorbent.
Wherein, the matrix material is porous substance-active carbon. The specific loading process comprises the following steps: dissolving amino adsorbate by using an organic solvent benzene, wherein the amino adsorbate and a matrix material are mixed according to a solid-to-liquid ratio (volume ratio) of 1: 0.2, stirring and mixing evenly, and keeping constant temperature for 6-24h under the vacuum condition of 70 ℃ to obtain the product of the embodiment.
Example 2
The preparation method of the amino formaldehyde adsorbent of the embodiment comprises the following steps:
s1, preparation of an intermediate:
dissolving caprolactam in benzene to prepare a solution 1; adding 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride into a reflux stirring device containing benzene, heating to 40 ℃, fully and uniformly mixing, dropwise adding the solution 1 into the reflux stirring device, and controlling the reaction temperature to be 55 ℃; after the dropwise addition is finished, heating to 80 ℃, refluxing, and continuously reacting for 3 hours; after the reaction is finished, removing unreacted reactants and solvent by rotary evaporation to obtain an intermediate;
in this step, the molar ratio of caprolactam to 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptylalkyl ] carbonyl chloride is 1: 0.5; the molar ratio of 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride to benzene in the reflux stirring device is 1: 1.
s2, preparing amino adsorbate:
dissolving the intermediate prepared in the step S1 in benzene, stirring and heating to 35 ℃, and slowly introducing excessive ammonia gas for reaction after complete mixing; after the reaction is finished, washing with water to remove entrained impurity NH 4 Br and NH 3 Turning roundEvaporating to remove solvent to obtain amino adsorbate;
in the step, the molar ratio of the intermediate to benzene is 1: 2.
s3, load: and loading the amino adsorbate on a base material to obtain the target product, namely the amino formaldehyde adsorbent. Wherein, the matrix material is porous substance-active carbon, and the following pretreatment is carried out: and keeping the mixture in a vacuum constant-temperature environment at 90 ℃ for 6 hours.
The specific loading process comprises the following steps: dissolving the amino adsorbate in an organic solvent ethyl acetate, and mixing the amino adsorbate with the pretreated matrix material according to a solid-to-liquid ratio of 1: 0.5, stirring and mixing uniformly, and keeping the constant temperature for 12 hours at 70 ℃ under a vacuum condition to obtain a target product.
Example 3
The preparation method of the amino formaldehyde adsorbent of the embodiment comprises the following steps:
s1, preparation of an intermediate:
dissolving caprolactam in benzene to prepare a solution 1; adding 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride into a reflux stirring device containing benzene, heating to 35 ℃, fully and uniformly mixing, then dropwise adding the solution 1 into the reflux stirring device, and controlling the reaction temperature to be 50 ℃; after the dropwise addition is finished, heating to 65 ℃ and refluxing, and continuing to react for 3 hours; after the reaction is finished, removing unreacted reactants and solvent by rotary evaporation to obtain an intermediate;
in this step, the molar ratio of caprolactam to 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptylalkyl ] carbonyl chloride is 1: 2; the molar ratio of 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride to benzene in the reflux stirring device is 1: 2.
s2, preparing amino adsorbate:
dissolving the intermediate prepared in the step S1 in benzene, stirring and heating to 35 ℃, and slowly introducing excessive ammonia gas for reaction after complete mixing; after the reaction is finished, washing with water to remove entrained impurity NH 4 Br and NH 3 Removing the solvent by rotary evaporation to obtain an amino adsorbate;
in the step, the molar ratio of the intermediate to benzene is 1: 4.
s3, load: and loading the amino adsorbate on a base material to obtain the target product, namely the amino formaldehyde adsorbent. Wherein, the matrix material is porous substance-active carbon, and is pretreated as follows: and keeping the mixture in a vacuum constant-temperature environment at 85 ℃ for 4 hours.
The specific loading process comprises the following steps: dissolving amino adsorbate by using an organic solvent benzene, and mixing the amino adsorbate with the pretreated matrix material according to a solid-to-liquid ratio of 1: 1, stirring and mixing uniformly, and keeping the constant temperature for 24 hours at 80 ℃ under a vacuum condition to obtain a target product.
Example 4
The preparation method of the amino formaldehyde adsorbent of the embodiment comprises the following steps:
s1, preparation of an intermediate:
dissolving caprolactam in benzene to prepare a solution 1; adding 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride into a reflux stirring device containing benzene, heating to 40 ℃, fully and uniformly mixing, then dropwise adding the solution 1 into the reflux stirring device, and controlling the reaction temperature to be 50 ℃; after the dropwise addition is finished, heating to 70 ℃, refluxing, and continuously reacting for 2 hours; after the reaction is finished, removing unreacted reactants and solvent by rotary evaporation to obtain an intermediate;
in this step, the molar ratio of caprolactam to 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptylalkyl ] carbonyl chloride is 1: 1; the molar ratio of 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride to benzene in the reflux stirring device is 1: 3.
s2, preparing amino adsorbate:
dissolving the intermediate prepared in the step S1 in benzene, stirring and heating to 35 ℃, and slowly introducing excessive ammonia gas for reaction after complete mixing; after the reaction is finished, washing with water to remove entrained impurity NH 4 Br and NH 3 Removing the solvent by rotary evaporation to obtain an amino adsorbate;
in the step, the molar ratio of the intermediate to benzene is 1: 3.
s3, load: and loading the amino adsorbate on a base material to obtain the target product, namely the amino formaldehyde adsorbent. Wherein, the matrix material is a porous substance-zeolite, and is pretreated as follows: and keeping the mixture in a vacuum constant-temperature environment at 80 ℃ for 5 hours.
The specific loading process comprises the following steps: dissolving amino adsorbate in organic solvent benzene, and mixing the amino adsorbate with the pretreated base material according to a solid-to-liquid ratio of 1: (0.2-1), stirring and mixing uniformly, and keeping constant temperature for 6-24 hours at the vacuum condition of 60-80 ℃ to obtain the target product.
Example 5
The preparation method of the amino formaldehyde adsorbent of the embodiment comprises the following steps:
s1, preparation of an intermediate:
dissolving caprolactam in benzene to prepare a solution 1; adding 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride into a reflux stirring device containing benzene, heating to 40 ℃, fully and uniformly mixing, dropwise adding the solution 1 into the reflux stirring device, and controlling the reaction temperature; after the dropwise addition is finished, heating to 80 ℃, refluxing, and continuously reacting for 3 hours; after the reaction is finished, removing unreacted reactants and solvent by rotary evaporation to obtain an intermediate;
in this step, the molar ratio of caprolactam to 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptylalkyl ] carbonyl chloride is 1: 0.5; the molar ratio of 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride to benzene in the reflux stirring device is 1: 1.
s2, preparing amino adsorbate:
dissolving the intermediate prepared in the step S1 in benzene, stirring and heating to 30 ℃, and slowly introducing excessive ammonia gas for reaction after complete mixing; after the reaction is finished, washing with water to remove entrained impurity NH 4 Br and NH 3 Removing the solvent by rotary evaporation to obtain an amino adsorbate;
in the step, the molar ratio of the intermediate to benzene is 1: 3.
s3, load: and loading the amino adsorbate on a base material to obtain the target product, namely the amino formaldehyde adsorbent. Wherein, the matrix material is porous substance-active carbon, and the porous substance is firstly modified: mixing a sodium carbonate solution and an ammonium chloride solution, soaking and boiling the porous substance at 70 ℃ for 12 hours, washing with dilute hydrochloric acid and deionized water in sequence, drying, transferring to a quartz boat, heating to 500 ℃, keeping the temperature for 4min, naturally cooling, and then pretreating: and keeping the mixture in a vacuum constant-temperature environment at 90 ℃ for 6 hours.
The specific loading process comprises the following steps: dissolving amino adsorbate by using an organic solvent benzene, and mixing the amino adsorbate with a modified and pretreated base material according to a solid-to-liquid ratio of 1: 0.8, stirring and mixing uniformly, and keeping constant temperature for 18 hours at the vacuum condition of 60 ℃ to obtain the target product.
Example 6
The preparation method of the amino-formaldehyde adsorbent of the embodiment comprises the following steps:
s1, preparation of an intermediate:
dissolving caprolactam in benzene to prepare a solution 1; adding 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride into a reflux stirring device containing benzene, heating to 35 ℃, fully and uniformly mixing, then dropwise adding the solution 1 into the reflux stirring device, and controlling the reaction temperature; after the dropwise addition is finished, heating to 70 ℃, refluxing, and continuously reacting for 2 hours; after the reaction is finished, removing unreacted reactants and solvent by rotary evaporation to obtain an intermediate;
in this step, the molar ratio of caprolactam to 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptylalkyl ] carbonyl chloride is 1: 1; the molar ratio of 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride to benzene in the reflux stirring device is 1: 2.
s2, preparing amino adsorbate:
dissolving the intermediate prepared in the step S1 in benzene, stirring and heating to 35 ℃, and slowly introducing excessive ammonia gas for reaction after complete mixing; after the reaction is finished, washing with water to remove entrained impurity NH 4 Br and NH 3 Removing the solvent by rotary evaporation to obtain an amino adsorbate;
in the step, the molar ratio of the intermediate to benzene is 1: 2.
s3, load: and loading the amino adsorbate on a base material to obtain the target product, namely the amino formaldehyde adsorbent. Wherein, the matrix material is a porous substance-zeolite, and the porous substance is firstly modified: mixing a sodium carbonate solution and an ammonium chloride solution, soaking and boiling the porous substance at 70 ℃ for 6 hours, washing with dilute hydrochloric acid and deionized water in sequence, drying, transferring to a quartz boat, heating to 400 ℃, keeping the temperature for 5min, naturally cooling, and then pretreating: and keeping the mixture in a vacuum constant-temperature environment at 80 ℃ for 6 hours.
The specific loading process comprises the following steps: dissolving amino adsorbate in an organic solvent ethyl acetate, and mixing the amino adsorbate with a modified and pretreated base material according to a solid-to-liquid ratio of 1: 1, stirring and mixing uniformly, and keeping the constant temperature for 9 hours at 70 ℃ under a vacuum condition to obtain a target product.
Example 7
The preparation method of the amino formaldehyde adsorbent of the embodiment comprises the following steps:
s1, preparation of an intermediate:
dissolving caprolactam in benzene to prepare a solution 1; adding 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride into a reflux stirring device containing benzene, heating to 35 ℃, fully and uniformly mixing, then dropwise adding the solution 1 into the reflux stirring device, and controlling the reaction temperature; after the dropwise addition is finished, heating to 80 ℃, refluxing, and continuously reacting for 2 hours; after the reaction is finished, removing unreacted reactants and solvent by rotary evaporation to obtain an intermediate;
in this step, the molar ratio of caprolactam to 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptylalkyl ] carbonyl chloride is 1: 2; the molar ratio of the 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride to the benzene in the reflux stirring device is 1: 3.
s2, preparing amino adsorbate:
dissolving the intermediate prepared in the step S1 in benzene, stirring and heating to 30 ℃, and slowly introducing excessive ammonia gas for reaction after complete mixing; after the reaction is finished, washing the reaction product by water to remove entrained impurity NH 4 Br and NH 3 Removing the solvent by rotary evaporation to obtain an amino adsorbate;
in the step, the molar ratio of the intermediate to benzene is 1: 4.
s3, load: and loading the amino adsorbate on a base material to obtain the target product, namely the amino formaldehyde adsorbent. Wherein, the matrix material is porous substance-active carbon, and the porous substance is firstly modified: mixing a sodium carbonate solution and an ammonium chloride solution, soaking and boiling the porous substance at 80 ℃ for 6h, washing with dilute hydrochloric acid and deionized water in sequence, drying, transferring to a quartz boat, heating to 600 ℃, keeping the temperature for 3min, naturally cooling, and then pretreating: and keeping the mixture in a vacuum constant-temperature environment at 85 ℃ for 5 hours.
The specific loading process comprises the following steps: dissolving amino adsorbate by using an organic solvent benzene, and mixing the amino adsorbate with a modified and pretreated base material according to a solid-to-liquid ratio of 1: 0.5, stirring and mixing uniformly, and keeping the constant temperature for 12 hours at 70 ℃ under a vacuum condition to obtain a target product.
Comparative example
The comparative example used a commercially available activated carbon adsorbent for adsorbing formaldehyde.
The target product prepared by the method of the embodiment 1-7 is the amino formaldehyde adsorbent, wherein the matrix material of the embodiment 1 is a common porous substance, namely activated carbon or zeolite; the base material of examples 2 to 4 was a porous material subjected to pretreatment; the base materials of examples 5 to 7 were porous materials that were modified and then pretreated.
To validate the products of each example, the following pairs were tested for structure and performance, respectively:
(1) the specific surface areas of the base materials used in examples 1 to 7 and comparative examples were measured by the BET method, and the results are shown in table 1.
(2) The target products of the examples were tested for 24h formaldehyde removal:
the specific detection method comprises the following steps: the adsorbents in the examples and the comparative examples are detected by adopting a gas chromatography or a spectrophotometry according to GB/T18204.26-2000 method for measuring formaldehyde in air in public places and GB/T18883-2002 standard for indoor environment quality, and the detection results are shown in the following table 1.
TABLE 1
As can be seen from the above, the BET specific surface area of the substrate material used in example 1 is substantially similar to that of the comparative example, but the 24h formaldehyde removal rate is much higher than that of the comparative example, and thus, the amino formaldehyde adsorbent obtained by loading the amino adsorbate onto the substrate material according to the present invention has a better selective adsorption capacity for formaldehyde, and the 24h formaldehyde removal rate is increased to 92%, and no secondary pollution is caused by decomposition.
After the base materials adopted in the embodiments 2-4 are pretreated, the BET specific surface area is improved to a certain extent compared with that of the embodiment 1; the matrix materials adopted in the embodiments 5 to 7 are firstly modified and then pretreated, so that the BET specific surface area is further remarkably improved. By combining electron microscope test results, it is found that after the substrate material of examples 5 to 7 is subjected to etching modification treatment, the number of internal mesopores (mesopores) and micropores is obviously increased, and the pore structure is etched more obviously. Thus, in the present invention, the sodium carbonate solution and the ammonium chloride solution achieve further pore-forming of the porous matrix material from a microscopic level, resulting in a higher BET specific surface area of the matrix material. As can be seen from the above table 1, the removal rate of 24h can be improved to more than 95% by adopting the pretreated porous substance as the matrix material; the removal rate of 24h can be stabilized to more than 98 percent by adopting the modified and pretreated porous substance as the matrix material.
(3) The penetration time and the formaldehyde adsorption amount of the product of each example in the normal temperature environment were measured by formaldehyde adsorption experiments, and the results are shown in table 2 below.
Wherein, when the penetration time is that the formaldehyde adsorption purification efficiency of the adsorbent is less than or equal to 90 percent, 200g of the adsorbent of each embodiment has the concentration of 1mg/m for formaldehyde 3 The working time of the air, which also represents the point since which the adsorbent substantially reached saturation for adsorbing formaldehyde, was actually measured using experimental equipment.
The adsorption capacity can be calculated by weighing the total mass of the adsorbent before and after adsorption.
TABLE 2
The results of the adsorption amount detection prove again that: the BET specific surface area of the matrix material plays a crucial role in promoting the formaldehyde adsorption quantity which is the adsorption effect. In the invention, the example 7 is the best example, the adsorption amount is up to 70.3mg/g, and the penetration time is up to 140h, which shows that the effective adsorption time of the formaldehyde is longer.
In conclusion, the preparation process of the amino formaldehyde adsorbent is simple, environment-friendly, safe and low in cost. By loading the amino adsorbate on the base material, the selectivity of the amino to formaldehyde is fully utilized, formaldehyde gas can be rapidly enriched on the surface of the adsorbent and subjected to chemical addition reaction, the aim of thoroughly removing formaldehyde is fulfilled, and secondary pollution can be effectively inhibited.
The substrate material modified and pretreated by a specific process can obviously improve the specific surface area of the porous substance, further improves the internal pore channel structure, realizes microcosmic pore-forming, further improves the loading capacity of the amine adsorbate and greatly optimizes the adsorption effect. The verification proves that the amino-formaldehyde adsorbent prepared by the process has excellent performance, the formaldehyde removal rate in 24 hours is basically stabilized to be more than 95%, the penetration time reaches 140 hours, and the adsorption capacity can reach more than 70 mg/g. The adsorbent has the characteristics of good water resistance and acid and alkali resistance, and the melting point is more than 70 ℃, so that the adsorbent shows a good formaldehyde adsorption effect in a high-temperature environment, a humid environment and an acid-alkali environment.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.
Claims (10)
1. The preparation method of the amino formaldehyde adsorbent is characterized by comprising the following steps:
s1, preparation of an intermediate:
dissolving caprolactam in benzene to prepare a solution 1; adding 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] formyl chloride into a reflux stirring device containing benzene, heating to 35-40 ℃, fully and uniformly mixing, then dropwise adding the solution 1 into the reflux stirring device, and controlling the reaction temperature; after the dropwise addition is finished, heating to 65-80 ℃, refluxing, and continuously reacting for 2-3 h; after the reaction is finished, removing unreacted reactants and solvent by rotary evaporation to obtain an intermediate;
s2, preparing amino adsorbate:
dissolving the intermediate prepared in the step S1 in benzene, stirring and heating to 30-35 ℃, and slowly introducing excessive ammonia gas for reaction after complete mixing; after the reaction is finished, washing with water to remove entrained impurity NH 4 Br and NH 3 Removing the solvent by rotary evaporation to obtain an amino adsorbate;
s3, load: and loading the amino adsorbate on a base material to obtain the target product, namely the amino formaldehyde adsorbent.
2. The method of claim 1, wherein in step S1, the molar ratio of caprolactam to 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] carbonyl chloride is 1: (0.5-2).
3. The method of claim 1, wherein in step S1, the molar ratio of 3- [2,6, 6-trimethyl-2-bromobicyclo [3.1.1] heptanyl ] carbonyl chloride to benzene in the reflux mixer is 1: (1-3).
4. The method according to claim 1, wherein in step S1, the reaction temperature is controlled to be 50-55 ℃.
5. The method of claim 1, wherein in step S2, the molar ratio of the intermediate to benzene is 1: (2-4).
6. The method for preparing the amino formaldehyde adsorbent according to claim 1, wherein in the step S3, the specific loading process is as follows: dissolving amino adsorbate by using an organic solvent, wherein the solid-liquid ratio of the amino adsorbate to a matrix material is 1: (0.2-1), stirring and mixing uniformly, and keeping constant temperature for 6-24 hours at the vacuum condition of 60-80 ℃ to obtain the target product.
7. The method according to any one of claims 1 to 6, wherein in step S3, the matrix material is a porous substance, and the porous substance is activated carbon or zeolite.
8. The method according to claim 7, wherein the porous material is pretreated by: and (4) keeping the mixture in a vacuum constant-temperature environment at 80-90 ℃ for 4-6 hours.
9. The method for preparing the amino formaldehyde adsorbent according to claim 8, wherein the porous substance is further modified before the pretreatment: mixing a sodium carbonate solution and an ammonium chloride solution, soaking and boiling the porous substance at 60-80 ℃ for 6-18 h, washing with dilute hydrochloric acid and deionized water in sequence, drying, transferring to a quartz boat, heating to 400-600 ℃, keeping the temperature for 3-5 min, naturally cooling, and then pretreating.
10. An amino-formaldehyde adsorbent produced by the production method according to any one of claims 1 to 9.
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| CN116239717A (en) * | 2023-05-12 | 2023-06-09 | 天津南开和成科技有限公司 | Functional resin for Mannich reaction and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090048085A (en) * | 2007-11-09 | 2009-05-13 | 학교법인 함주학원 | A production method of aminated sorbent |
| CN101468305A (en) * | 2007-12-29 | 2009-07-01 | 中国船舶重工集团公司第七一八研究所 | Methyl aldehyde adsorbing substance and preparation method thereof |
| CN103088464A (en) * | 2013-02-01 | 2013-05-08 | 湖北工业大学 | Preparation method of porous boron nitrite fibers |
| CN104741130A (en) * | 2013-12-27 | 2015-07-01 | 江苏瑞丰科技实业有限公司 | Normal temperature formaldehyde removal catalysis material |
| CN110280311A (en) * | 2019-06-27 | 2019-09-27 | 济南大学 | A kind of preparation method of porous buckwheat skin load photocatalyst formaldehyde scavenger |
| CN112934183A (en) * | 2021-02-07 | 2021-06-11 | 扬州工业职业技术学院 | Organic waste gas adsorbent and preparation method thereof |
-
2022
- 2022-06-16 CN CN202210679003.7A patent/CN115041139A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090048085A (en) * | 2007-11-09 | 2009-05-13 | 학교법인 함주학원 | A production method of aminated sorbent |
| CN101468305A (en) * | 2007-12-29 | 2009-07-01 | 中国船舶重工集团公司第七一八研究所 | Methyl aldehyde adsorbing substance and preparation method thereof |
| CN103088464A (en) * | 2013-02-01 | 2013-05-08 | 湖北工业大学 | Preparation method of porous boron nitrite fibers |
| CN104741130A (en) * | 2013-12-27 | 2015-07-01 | 江苏瑞丰科技实业有限公司 | Normal temperature formaldehyde removal catalysis material |
| CN110280311A (en) * | 2019-06-27 | 2019-09-27 | 济南大学 | A kind of preparation method of porous buckwheat skin load photocatalyst formaldehyde scavenger |
| CN112934183A (en) * | 2021-02-07 | 2021-06-11 | 扬州工业职业技术学院 | Organic waste gas adsorbent and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116239717A (en) * | 2023-05-12 | 2023-06-09 | 天津南开和成科技有限公司 | Functional resin for Mannich reaction and preparation method and application thereof |
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