CN113304727B - Preparation method of formaldehyde purification activated carbon with low cost and high activity - Google Patents
Preparation method of formaldehyde purification activated carbon with low cost and high activity Download PDFInfo
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Abstract
The invention discloses a preparation method of formaldehyde purification activated carbon with low cost and high activity, which comprises the following steps: s1: preparing an impregnating solution containing high boiling point acid and organic amine; s2: the impregnating solution obtained in the step S1 is impregnated with active carbon in an equal volume to obtain impregnated active carbon; s3: and (3) spreading, ventilating and air-drying the impregnated activated carbon obtained in the step (S2) to obtain the formaldehyde purification activated carbon. In step S1, the high boiling point acid includes one or a mixture of two of sulfuric acid and phosphoric acid. Compared with the prior art, the invention adopts the active carbon nano pore canal liquid phase film forming, the introduction of high boiling point acid greatly strengthens and accelerates the mass transfer process of formaldehyde molecules to the aqueous phase liquid film, so that formaldehyde and organic amine react rapidly in the liquid phase, and the purification efficiency of formaldehyde is greatly improved; meanwhile, the whole process is simple and convenient to operate, a high-temperature drying process is avoided, and the production cost is greatly reduced.
Description
Technical Field
The invention relates to a preparation method of formaldehyde purification activated carbon with low cost and high activity, belonging to the field of air purification.
Background
Formaldehyde is a highly toxic gas that has been identified by the world health organization international cancer research institute IARC as a class 1 carcinogen. The limit value of formaldehyde in indoor air of class II civil building engineering specified in GB/T18883-2002 of indoor air quality standard of China is 0.10mg/m 3 The limit value of formaldehyde in indoor air of civil building engineering is 0.08mg/m 3 . The main hazard of formaldehyde is the stimulation to skin mucosa, and when formaldehyde reaches a certain concentration indoors, people feel uncomfortable. Greater than 0.08mg/m 3 Can cause redness, itching, throat discomfort or pain, hoarseness, sneeze, chest distress, asthma, dermatitis, etc. in short term; the long-term contact of the human body with low-concentration formaldehyde is extremely easy to cause nervous system disorder, memory decline, nasopharyngeal carcinoma, colon cancer and the like.
For the treatment of indoor formaldehyde pollution, different purification methods and purification materials are developed, and mainly comprise the following steps: the active carbon adsorption method utilizes the pore structure rich in active carbon to physically adsorb formaldehyde in the air, and has the defects of low adsorption capacity, easy saturation, secondary pollution caused by formaldehyde release after long-term use and the like; the spraying method is characterized in that nano titanium dioxide or formaldehyde scavenger is dissolved in a water phase system and sprayed in air to achieve the purpose of purifying formaldehyde, and the defect is that formaldehyde gas released continuously in a room cannot be purified continuously; the catalytic method is that active metals such as Mn, pd, pt and the like are loaded on a porous material, and formaldehyde is effectively decomposed into water and carbon dioxide by utilizing the catalytic activity of the active metals; the absorption method is to load formaldehyde scavenger into porous material and utilize chemical reaction of formaldehyde and scavenger to eliminate formaldehyde. Among the many methods, the absorption method is one of the means that is relatively effective in purifying formaldehyde in a room.
The national standard GB/T18801-2015 puts forward higher and stricter requirements on formaldehyde in an air purifier treatment chamber, so that the purification efficiency of a purification material on target pollutants is required to be inspected, and the accumulated purification capacity under long-term use is also required to be inspected. The existing absorption method material is difficult to combine the purification efficiency and the accumulated purification capability of formaldehyde under the specified test condition, and the complicated preparation process greatly increases the cost of the material.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for preparing formaldehyde purification activated carbon with low cost and high activity.
The aim of the invention is achieved by the following technical scheme: the preparation method of formaldehyde purification activated carbon with low cost and high activity comprises the following steps:
s1: preparing an impregnating solution containing high boiling point acid and organic amine;
s2: the impregnating solution obtained in the step S1 is impregnated with active carbon in an equal volume to obtain impregnated active carbon;
s3: and (3) spreading, ventilating and air-drying the impregnated activated carbon obtained in the step (S2) to obtain the formaldehyde purification activated carbon.
Preferably, in the step S1, the high boiling point acid includes one or a mixture of two of sulfuric acid and phosphoric acid.
Preferably, in the step S1, the organic amine includes one or more of ethylene urea, diethylamine, diethylenetriamine, triethylenetetramine and amino acids; wherein the amino acid substance comprises: glycine, aspartic acid, glutamic acid, cysteine, lysine, histidine, arginine.
Preferably, in the step S2, the mass ratio of the high boiling point acid to the activated carbon is 0.1-1.0:10; the mass ratio of the organic amine to the activated carbon is 0.1-1.0:15, and the dipping time is 6-24 hours; in the step S2, the equal volume impregnation is carried out, and the proportioning volume of the impregnation liquid is calculated according to the required saturated water absorption rate of the activated carbon.
Preferably, in the step S3, the activated carbon is tiled, ventilated and air-dried, in order to evenly and flatly spread the impregnated activated carbon under the condition of room temperature, natural ventilation is performed to volatilize partial moisture adsorbed by the activated carbon, the air-drying time is determined according to the room temperature, and sampling and weighing are performed until the moisture content in the material is 20-40%, so that the formaldehyde purification activated carbon is prepared.
Preferably, 100g of columnar coal activated carbon is weighed, and the saturated water absorption rate is 76% of the mass of the columnar coal activated carbon; weighing 76ml of deionized water in a beaker, weighing 5g of sulfuric acid and 5g of ethylene urea, and dissolving to prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and standing for 12 hours; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 28 ℃, and weighing 159g of the activated carbon after airing for 6 hours, wherein the water content of the material is 31%.
Preferably, 100g of columnar coal activated carbon is weighed, and the saturated water absorption rate is 76% of the mass of the columnar coal activated carbon; weighing 76ml of deionized water in a beaker, weighing 3g of phosphoric acid and 6g of glycine, and dissolving to prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and standing for 10 hours; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 30 ℃, and weighing the mass of the activated carbon to 145g after airing for 6 hours, wherein the water content of the material is 25%.
Preferably, 100g of coconut shell activated carbon is weighed, and the saturated water absorption rate is 70% of the mass of the coconut shell activated carbon; weighing 70ml of deionized water in a beaker, and weighing 3g of phosphoric acid, 3g of sulfuric acid and 8g of diethylamine for dissolution to prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and standing for 8 hours; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 28 ℃, and weighing the mass of the activated carbon after airing for 6 hours to obtain 158g, and the water content of the material is 28%.
Preferably, 100g of coconut shell activated carbon is weighed, and the saturated water absorption rate is 70% of the mass of the coconut shell activated carbon; weighing 70ml of deionized water in a beaker, weighing 8g of sulfuric acid and 10g of glutamic acid, and dissolving to prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and standing for 24 hours; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 25 ℃, and weighing the mass of the activated carbon to 176g after airing for 6 hours, wherein the water content of the material is 33%.
Preferably, 100g of coconut shell activated carbon is weighed, and the saturated water absorption rate is 70% of the mass of the coconut shell activated carbon; weighing 70ml of deionized water in a beaker, and weighing 7g of sulfuric acid, 5g of ethylene urea and 4g of glycine to dissolve and prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and standing for 18 hours; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 26 ℃, and weighing the mass of the activated carbon to 145g after airing for 10 hours, wherein the water content of the material is 20%.
The technical scheme of the invention has the advantages that: the method overcomes the defects of low adsorption capacity and easy saturation of active carbon and low reaction efficiency of gas (formaldehyde) -solid (formaldehyde scavenger) after the active carbon loaded formaldehyde scavenger is subjected to high-temperature drying treatment in the prior art, and utilizes the liquid phase film formation of the active carbon, the rapid adsorption of the active carbon residual pore canal to formaldehyde gas, the mass transfer of an acidic environment reinforced formaldehyde-liquid film to enable formaldehyde to be rapidly dissolved in the liquid film, and the efficient reaction process of liquid (formaldehyde) -liquid (organic amine formaldehyde scavenger) to prepare the high-activity formaldehyde purification active carbon at lower cost.
Compared with the prior art, the invention adopts the active carbon nano pore canal liquid phase film forming, the introduction of high boiling point acid greatly strengthens and accelerates the mass transfer process of formaldehyde molecules to the aqueous phase liquid film, so that formaldehyde and organic amine react rapidly in the liquid phase, and the purification efficiency of formaldehyde is greatly improved; meanwhile, the whole process is simple and convenient to operate, a high-temperature drying process is avoided, and the production cost is greatly reduced.
Detailed Description
The objects, advantages and features of the present invention will be explained by the following non-limiting description of preferred embodiments. These embodiments are only typical examples of the technical scheme of the invention, and all technical schemes formed by adopting equivalent substitution or equivalent transformation fall within the scope of the invention.
The invention discloses a preparation method of formaldehyde purification activated carbon with low cost and high activity, and the high activity is embodied in that the prepared material can quickly, efficiently and permanently eliminate indoor formaldehyde. The method is characterized in that high boiling point acid and organic amine substances are dissolved in a water phase and are carried by the same volume of activated carbon in an impregnating way, the water content of the material is 20-40% after natural air drying, part of water vapor escapes during the air drying process of the material, so that the material still has a developed pore structure, meanwhile, the impregnating liquid spreads in micro pore channels of the activated carbon to form a uniform liquid film, formaldehyde molecules in the air are quickly adsorbed by utilizing the porous structure of the material, the mass transfer absorption process of the formaldehyde molecules to the liquid film is intensified by utilizing an acidic environment, and finally, the purpose of quickly, efficiently and permanently eliminating the formaldehyde is achieved by utilizing the liquid-liquid reaction of the organic amine and the formaldehyde.
The preparation method of the formaldehyde purification activated carbon with low cost and high activity comprises the following steps:
s1: preparing an impregnating solution containing high boiling point acid and organic amine;
s2: the impregnating solution obtained in the step S1 is impregnated with active carbon in an equal volume to obtain impregnated active carbon;
s3: and (3) spreading, ventilating and air-drying the impregnated activated carbon obtained in the step (S2) to obtain the formaldehyde purification activated carbon.
In the present embodiment, the concentration of the high boiling acid is not particularly specified, and since the amount of water required for the isovolumetric impregnation is different for different activated carbons, only the amount of high boiling acid used and the amount of water required for the isovolumetric impregnation are mentioned. In addition, no molar ratio is mentioned here, only the mass ratio is used. Wherein, the high boiling point acid refers to one or two of sulfuric acid and sulfuric acid; the organic amine comprises one or more of diethylamine, diethylenetriamine, triethylenetetramine and amino acids. Wherein the amino acid substance comprises: glycine, aspartic acid, glutamic acid, cysteine, lysine, histidine, arginine. Preparing a mixed impregnating solution of high-boiling-point acid and organic amine according to the volume of a solution required by isovolumetric impregnation according to the difference of saturated water absorption rates of the activated carbon, wherein the mass ratio of the high-boiling-point acid to the activated carbon is 0.1-1.0:10; the mass ratio of the organic amine to the activated carbon is 0.1-1.0:10, and the soaking time is generally 6-24 hours.
After the impregnation is finished, uniformly spreading the impregnated activated carbon at room temperature, naturally ventilating to volatilize partial water adsorbed by the activated carbon, and taking samples and weighing until the water content in the material is 20-40% according to the temperature of the room temperature during air drying, thus obtaining the formaldehyde purification activated carbon.
Example 1
Weighing 100g of coal columnar activated carbon, wherein in the technical scheme, no special requirement is generally imposed on activated carbon particles, and the saturated water absorption rate is 76% of the mass of the activated carbon particles as long as the activated carbon particles are not in powder form; weighing 76ml of deionized water in a beaker, weighing 5g of sulfuric acid and 5g of ethylene urea, and dissolving to prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and standing for 12 hours; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 28 ℃, and weighing 159g of the activated carbon after airing for 6 hours, wherein the water content of the material is 31%.
A sample without adding high boiling point acid was prepared by the same method, and the rest of the preparation process was the same. The following examples also prepare samples without the addition of high boiling acids according to the process conditions.
Example 2
Weighing 100g of coal columnar activated carbon, wherein the saturated water absorption rate of the columnar activated carbon is 76% of the mass of the columnar activated carbon; weighing 76ml of deionized water in a beaker, weighing 3g of phosphoric acid and 6g of glycine, and dissolving to prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and standing for 10 hours; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 30 ℃, and weighing the mass of the activated carbon to 145g after airing for 6 hours, wherein the water content of the material is 25%.
Example 3
Weighing 100g of coconut shell activated carbon, wherein the saturated water absorption rate of the coconut shell activated carbon is 70% of the mass of the coconut shell activated carbon; weighing 70ml of deionized water in a beaker, and weighing 3g of phosphoric acid, 3g of sulfuric acid and 8g of diethylamine for dissolution to prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and standing for 8 hours; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 28 ℃, and weighing the mass of the activated carbon after airing for 6 hours to obtain 158g, and the water content of the material is 28%.
Example 4
Weighing 100g of coconut shell activated carbon, wherein the saturated water absorption rate of the coconut shell activated carbon is 70% of the mass of the coconut shell activated carbon; weighing 70ml of deionized water in a beaker, weighing 8g of sulfuric acid and 10g of glutamic acid, and dissolving to prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and standing for 24 hours; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 25 ℃, and weighing the mass of the activated carbon to 176g after airing for 6 hours, wherein the water content of the material is 33%.
Example 5
Weighing 100g of coconut shell activated carbon, wherein the saturated water absorption rate of the coconut shell activated carbon is 70% of the mass of the coconut shell activated carbon; weighing 70ml of deionized water in a beaker, and weighing 7g of sulfuric acid, 5g of ethylene urea and 4g of glycine to dissolve and prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and standing for 18 hours; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 26 ℃, and weighing the mass of the activated carbon to 145g after airing for 10 hours, wherein the water content of the material is 20%.
In order to verify the feasibility of the formaldehyde purification activated carbon prepared by the invention applied to indoor air treatment, the air quantity is 15m 3 A self-made mini-purifier per hour was charged with about 50g of formaldehyde-purifying activated carbon and placed in 1M 3 The experimental cabin is provided with a plurality of test chambers; dripping formaldehyde into the experimental cabin to balance the formaldehyde in the cabin to 1.0+/-0.2 mg/m 3 (initial concentration)Selecting 10±2 times the concentration limit specified in GB/T18883); and (3) starting a power switch of the purifier, starting the purifier to work, sampling the concentration of formaldehyde in the test cabin after timing for 1 hour, and calculating the formaldehyde purification efficiency.
Note that: the formaldehyde concentration was measured by chemical absorption.
The formaldehyde purification activated carbon prepared by the invention has the following advantages: 1) The operation is simple and convenient, and the acid and alkali pretreatment of the activated carbon is not needed; 2) No high-temperature operation flow is adopted, and the activated carbon is naturally air-dried at room temperature after being impregnated with high-boiling-point acid and organic amine; 3) The preparation cost of the formaldehyde purification activated carbon is greatly reduced; 4) The formaldehyde purification activated carbon with higher activity is prepared by coupling the technology of activated carbon rapid adsorption, acid environment enhanced formaldehyde-liquid membrane mass transfer, formaldehyde and organic amine liquid reaction
In addition to the above embodiments, other embodiments of the present invention are possible, and all technical solutions formed by equivalent substitution or equivalent transformation are within the scope of the present invention as claimed.
Claims (8)
1. A preparation method of formaldehyde purification activated carbon with low cost and high activity is characterized in that: the method comprises the following steps:
s1: preparing an impregnating solution containing high boiling point acid and organic amine;
s2: the impregnating solution obtained in the step S1 is impregnated with active carbon in an equal volume to obtain impregnated active carbon;
s3: spreading, ventilating and air-drying the impregnated activated carbon obtained in the step S2 to obtain formaldehyde purification activated carbon; in the step S2, the mass ratio of the high boiling point acid to the activated carbon is 0.1-1.0:10; the mass ratio of the organic amine to the activated carbon is 0.1-1.0:15, and the dipping time is 6-24 hours; in the step S2, the equal volume impregnation is carried out, and the proportioning volume of the impregnation liquid is calculated according to the required saturated water absorption rate of the activated carbon;
in the step S3, the activated carbon is paved, ventilated and air-dried, the impregnated activated carbon is evenly paved under the condition of room temperature, natural ventilation is carried out to volatilize partial moisture adsorbed by the activated carbon, the air-drying time is determined according to the room temperature, and sampling and weighing are carried out until the moisture content in the material is 20-40%, so that the formaldehyde purification activated carbon is prepared.
2. The method for preparing formaldehyde purification activated carbon with low cost and high activity according to claim 1, which is characterized in that: in the step S1, the high boiling point acid includes one or a mixture of two of sulfuric acid and phosphoric acid.
3. The method for preparing formaldehyde purification activated carbon with low cost and high activity according to claim 1, which is characterized in that: in the step S1, the organic amine comprises one or more of ethylene urea, diethylamine, diethylenetriamine, triethylenetetramine and amino acid substances; wherein the amino acid substance comprises: glycine, aspartic acid, glutamic acid, cysteine, lysine, histidine, arginine.
4. The method for preparing formaldehyde purification activated carbon with low cost and high activity according to claim 1, which is characterized in that: weighing 100g coal columnar activated carbon, wherein the saturated water absorption rate of the activated carbon is 76% of the mass of the activated carbon; weighing 76ml deionized water in a beaker, weighing 5g sulfuric acid and 5g ethylene urea, and dissolving to prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and then placing 12h; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 28 ℃, and weighing the mass of the activated carbon after airing for 6 hours to obtain 159g, wherein the water content of the material is 31%.
5. The method for preparing formaldehyde purification activated carbon with low cost and high activity according to claim 1, which is characterized in that: weighing 100g coal columnar activated carbon, wherein the saturated water absorption rate of the activated carbon is 76% of the mass of the activated carbon; weighing 76ml deionized water in a beaker, weighing 3g phosphoric acid and 6g glycine, and dissolving to prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and then placing 10h; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 30 ℃, and weighing the mass of the activated carbon after airing for 6 hours to be 145g, wherein the water content of the material is 25%.
6. The method for preparing formaldehyde purification activated carbon with low cost and high activity according to claim 1, which is characterized in that: weighing 100g coconut shell activated carbon, wherein the saturated water absorption rate of the coconut shell activated carbon is 70% of the mass of the coconut shell activated carbon; weighing 70ml deionized water in a beaker, and weighing 3g phosphoric acid, 3g sulfuric acid and 8g diethylamine for dissolution to prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and then placing 8h; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 28 ℃, and weighing the mass of the activated carbon after airing for 6 hours to obtain 158-g, wherein the water content of the material is 28%.
7. The method for preparing formaldehyde purification activated carbon with low cost and high activity according to claim 1, which is characterized in that: weighing 100g coconut shell activated carbon, wherein the saturated water absorption rate of the coconut shell activated carbon is 70% of the mass of the coconut shell activated carbon; weighing 70ml deionized water in a beaker, weighing 8g sulfuric acid and 10g glutamic acid, and dissolving to prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and then placing 24-h; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 25 ℃, and weighing the mass of the activated carbon after airing for 6 hours to be 176g, wherein the water content of the material is 33%.
8. The method for preparing formaldehyde purification activated carbon with low cost and high activity according to claim 1, which is characterized in that: weighing 100g coconut shell activated carbon, wherein the saturated water absorption rate of the coconut shell activated carbon is 70% of the mass of the coconut shell activated carbon; weighing 70ml deionized water in a beaker, and weighing 7g sulfuric acid, 5g ethylene urea and 4g glycine to dissolve and prepare an impregnating solution; mixing the impregnating solution with the activated carbon, uniformly stirring, and then placing 18-h; spreading the activated carbon on a screen, naturally airing, wherein the indoor temperature is 26 ℃, and weighing the mass of the activated carbon after airing for 10 hours to be 145g, wherein the water content of the material is 20%.
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