CN113304727A - 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 impregnation liquid containing high-boiling-point acid and organic amine; s2: soaking the soaking solution obtained in the step S1 and activated carbon in equal volume to obtain soaked activated carbon; s3: and (4) flatly laying the impregnated activated carbon obtained in the step S2, ventilating and air-drying to obtain the formaldehyde purification activated carbon. In step S1, the high boiling acid includes one or two of sulfuric acid and phosphoric acid. Compared with the prior art, the method adopts the active carbon nano-pore liquid phase to form the film, and the introduction of the high-boiling-point acid greatly strengthens and accelerates the mass transfer process of formaldehyde molecules to the water phase liquid film, so that the formaldehyde and the organic amine are quickly reacted in the liquid phase, and the purification efficiency of the 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 and has been identified as a class 1 carcinogen by the International agency for research on cancer, IARC, the world health organization. China 'indoor air quality Standard' GB/T18883-2002 stipulates that the limit value of formaldehyde in indoor air of the second type of civil construction engineering is 0.10 mg/m for cultivation, and the limit value of formaldehyde in indoor air of the first type of civil construction engineering is 0.08 mg/m for cultivation. The main harm of formaldehyde is represented by stimulation to skin mucosa, and when the formaldehyde reaches a certain concentration indoors, people feel uncomfortable. A formaldehyde concentration higher than 0.08 mg/m can cause redness of the eye, itching of the eye, discomfort or pain in the throat, hoarseness, sneezing, chest distress, asthma, dermatitis and the like in a short period; and the long-term exposure of human body to low-concentration formaldehyde can easily cause nervous system disorder, memory decline, nasopharyngeal carcinoma, colon cancer and the like.
For the treatment of indoor formaldehyde pollution, people develop different purification methods and purification materials, mainly comprising: the active carbon adsorption method physically adsorbs formaldehyde in the air by utilizing a porous structure rich in active carbon, and has the defects of low adsorption capacity, easiness in 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 a formaldehyde catching agent is dissolved in a water phase system and sprayed in the air to achieve the purpose of purifying formaldehyde, and the defect is that the formaldehyde gas continuously released in a room can not be continuously purified; a catalytic method, in which 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 in porous material and utilize the chemical reaction between formaldehyde and scavenger to eliminate formaldehyde. Among the many methods, the absorption method is one of the more effective means for purifying formaldehyde in a room.
The national standard GB/T18801-. The existing absorption method material is difficult to consider the purification efficiency and the accumulative purification capacity of formaldehyde under the specified test condition, and the complex preparation process greatly increases the material cost.
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 purpose of the invention is realized by the following technical scheme: a preparation method of formaldehyde purification activated carbon with low cost and high activity comprises the following steps:
s1: preparing an impregnation liquid containing high-boiling-point acid and organic amine;
s2: soaking the soaking solution obtained in the step S1 and activated carbon in equal volume to obtain soaked activated carbon;
s3: and (4) flatly laying the impregnated activated carbon obtained in the step S2, ventilating and air-drying to obtain the formaldehyde purification activated carbon.
Preferably, in the S1 step, the high-boiling 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 substances comprise: glycine, aspartic acid, glutamic acid, cysteine, lysine, histidine and 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 active carbon is 0.1-1.0:15, and the soaking time is 6-24 hours; in the step S2, the equal volume of the impregnation solution is calculated according to the saturated water absorption of the required activated carbon.
Preferably, in the step S3, the activated carbon is spread flat and ventilated for air drying, in order to spread the impregnated activated carbon evenly and flat at room temperature, natural ventilation is performed to volatilize part of the moisture absorbed by the activated carbon, and the air drying time is determined according to the temperature at room temperature, and the sample is weighed until the moisture content in the material is 20-40%, so as to prepare the formaldehyde purification activated carbon.
Preferably, 100 g of coal columnar activated carbon is weighed, and the saturated water absorption rate of the coal columnar activated carbon is 76% of the mass of the coal columnar activated carbon; weighing 76 ml of deionized water in a beaker, weighing 5 g of sulfuric acid and 5 g of ethylene urea, and dissolving to prepare a dipping solution; mixing the impregnation liquid with the activated carbon, uniformly stirring, and standing for 12 h; the activated carbon was spread on a screen and air dried naturally at an indoor temperature of 28 ℃ for 6 hours, and the mass of the activated carbon was 159 g, at which time the water content of the material was 31%.
Preferably, 100 g of coal columnar activated carbon is weighed, and the saturated water absorption rate of the coal columnar activated carbon is 76% of the mass of the coal columnar activated carbon; weighing 76 ml of deionized water in a beaker, weighing 3 g of phosphoric acid and 6 g of glycine, and dissolving to prepare a steeping fluid; mixing the impregnation liquid with the active carbon, uniformly stirring, and standing for 10 h; the activated carbon is laid on a screen mesh and naturally dried at the indoor temperature of 30 ℃ for 6 hours, and the weight of the activated carbon is 145 g, and the water content of the material is 25%.
Preferably, 100 g of coconut shell activated carbon is weighed, and the saturated water absorption rate of the coconut shell activated carbon is 70% of the mass of the coconut shell activated carbon; weighing 70 ml of deionized water in a beaker, weighing 3 g of phosphoric acid, 3 g of sulfuric acid and 8 g of diethylamine, and dissolving to prepare a dipping solution; mixing the impregnation liquid with the active carbon, uniformly stirring, and standing for 8 hours; the activated carbon was spread on a screen and air dried naturally at an indoor temperature of 28 ℃ for 6 hours, and the mass of the activated carbon was 158 g, at which time the water content of the material was 28%.
Preferably, 100 g of coconut shell activated carbon is weighed, and the saturated water absorption rate of the coconut shell activated carbon is 70% of the mass of the coconut shell activated carbon; weighing 70 ml of deionized water in a beaker, and weighing 8 g of sulfuric acid and 10 g of glutamic acid to dissolve to prepare a steeping fluid; mixing the impregnation liquid with the activated carbon, uniformly stirring, and standing for 24 hours; the activated carbon was spread on a screen and air dried naturally at 25 ℃ in room temperature for 6 hours, and the mass of the activated carbon was 176 g, at which time the water content of the material was 33%.
Preferably, 100 g of coconut shell activated carbon is weighed, and the saturated water absorption rate of the coconut shell activated carbon is 70% of the mass of the coconut shell activated carbon; weighing 70 ml of deionized water in a beaker, weighing 7 g of sulfuric acid, 5 g of ethylene urea and 4 g of glycine, and dissolving to prepare a dipping solution; mixing the impregnation liquid with the activated carbon, uniformly stirring, and standing for 18 h; the activated carbon is laid on a screen mesh and naturally dried at the indoor temperature of 26 ℃ for 10 hours, and the weight of the activated carbon is 145 g, and 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 the 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 prepares the high-activity formaldehyde purification active carbon at lower cost by utilizing the processes of liquid-phase film formation of the active carbon, rapid adsorption of residual pore channels of the active carbon on the formaldehyde gas, and mass transfer strengthening of a formaldehyde-liquid film in an acidic environment so as to rapidly dissolve the formaldehyde in the liquid film and high-efficiency reaction of the liquid (formaldehyde) -liquid (organic amine formaldehyde scavenger).
Compared with the prior art, the method adopts the active carbon nano-pore liquid phase to form the film, and the introduction of the high-boiling-point acid greatly strengthens and accelerates the mass transfer process of formaldehyde molecules to the water phase liquid film, so that the formaldehyde and the organic amine are quickly reacted in the liquid phase, and the purification efficiency of the 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 illustrated by the following non-limiting description of preferred embodiments. The embodiments are merely exemplary for applying the technical solutions of the present invention, and any technical solution formed by replacing or equivalently transforming the embodiments is within the scope of the present invention as claimed.
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 durably eliminate indoor formaldehyde. Dissolving high-boiling-point acid and organic amine substances into a water phase, impregnating and loading the materials with active carbon in an equal volume, naturally drying the materials until the water content of the materials is 20-40%, allowing part of water vapor to escape in the air drying process of the materials to enable the materials to still have a developed pore structure, spreading impregnation liquid in a micro pore channel of the active carbon to form a uniform liquid film, quickly adsorbing formaldehyde molecules in the air by using the porous structure of the materials, strengthening the mass transfer absorption process of the formaldehyde molecules to the liquid film by using an acidic environment, and finally performing liquid-liquid reaction of organic amine and formaldehyde to achieve the aim of quickly, efficiently and durably eliminating the formaldehyde.
A preparation method of formaldehyde purification activated carbon with low cost and high activity comprises the following steps:
s1: preparing an impregnation liquid containing high-boiling-point acid and organic amine;
s2: soaking the soaking solution obtained in the step S1 and activated carbon in equal volume to obtain soaked activated carbon;
s3: and (4) flatly laying the impregnated activated carbon obtained in the step S2, ventilating and air-drying to obtain the formaldehyde purification activated carbon.
In the technical scheme, the concentration of the high-boiling-point acid is not particularly specified, and because different activated carbons require different water amounts when equal-volume impregnation is carried out, only the use amount of the high-boiling-point acid and the water amount required by equal-volume impregnation are mentioned. In addition, the molar ratios are not mentioned here, but are used only in mass ratios. Wherein, the high boiling point acid refers to one or a mixture of sulfuric acid and sulfuric acid; the organic amine comprises one or more of diethylamine, diethylenetriamine, triethylene tetramine and amino acid substances. Wherein, the amino acid substances comprise: glycine, aspartic acid, glutamic acid, cysteine, lysine, histidine and arginine.
Preparing a high-boiling-point acid and organic amine mixed impregnation liquid according to the volume of a solution required by equal volume impregnation according to the difference of saturated water absorption 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 impregnation time is generally 6-24 hours.
After the impregnation is finished, uniformly and flatly spreading the impregnated activated carbon at room temperature, naturally ventilating to volatilize part of water absorbed by the activated carbon, sampling and weighing until the water content in the material is 20-40% according to the room temperature, and thus obtaining the formaldehyde purification activated carbon.
Example 1
100 g of coal columnar activated carbon is weighed, in the technical scheme, no special requirement is generally made on activated carbon particles, as long as the activated carbon particles are not powdery, and the saturated water absorption of the activated carbon particles is 76 mass percent of the activated carbon particlesPercent; weighing 76 ml of deionized water in a beaker, weighing 5 g of sulfuric acid and 5 g of ethylene urea, and dissolving to prepare a dipping solution; mixing the impregnation liquid with the activated carbon, uniformly stirring, and standing for 12 h; spreading activated carbon on a screen, air drying, and indoor temperature 28oC, after air-drying for 6 hours, the mass of the activated carbon was 159 g, and the water content of the material at this time was 31%.
A sample without the addition of the high-boiling acid was prepared in the same manner, and the remaining preparation processes were the same. The following examples were also prepared under the same process conditions as those of the above examples without adding a high boiling acid.
Example 2
Weighing 100 g of coal columnar activated carbon, wherein the saturated water absorption of the coal columnar activated carbon is 76% of the mass of the coal columnar activated carbon; weighing 76 ml of deionized water in a beaker, weighing 3 g of phosphoric acid and 6 g of glycine, and dissolving to prepare a steeping fluid; mixing the impregnation liquid with the active carbon, uniformly stirring, and standing for 10 h; spreading activated carbon on a screen, naturally drying at an indoor temperature of 30 deg.CoC, after air-drying for 6 hours, the mass of the activated carbon was 145 g, and the water content of the material at this time was 25%.
Example 3
Weighing 100 g 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 70 ml of deionized water in a beaker, weighing 3 g of phosphoric acid, 3 g of sulfuric acid and 8 g of diethylamine, and dissolving to prepare a dipping solution; mixing the impregnation liquid with the active carbon, uniformly stirring, and standing for 8 hours; spreading activated carbon on a screen, air drying, and indoor temperature 28oC, after air-drying for 6 hours, the mass of the activated carbon was 158 g, and the water content of the material at this time was 28%.
Example 4
Weighing 100 g 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 70 ml of deionized water in a beaker, and weighing 8 g of sulfuric acid and 10 g of glutamic acid to dissolve to prepare a steeping fluid; mixing the impregnation liquid with the activated carbon, uniformly stirring, and standing for 24 hours; spreading activated carbon on a screen, naturally drying at an indoor temperature of 25 deg.CoC, after air-drying for 6 hours, the mass of the activated carbon was 176 g, and the water content of the material at this time was 33%.
Example 5
Weighing 100 g of coconut shellActivated carbon, the saturated water absorption of which is 70% of its mass; weighing 70 ml of deionized water in a beaker, weighing 7 g of sulfuric acid, 5 g of ethylene urea and 4 g of glycine, and dissolving to prepare a dipping solution; mixing the impregnation liquid with the activated carbon, uniformly stirring, and standing for 18 h; spreading the activated carbon on a screen, air drying naturally, and keeping the indoor temperature at 26 deg.CoC, after air-drying for 10 hours, the mass of the activated carbon was 145 g, and the water content of the material at this time was 20%.
In order to verify the feasibility of applying the formaldehyde purification activated carbon prepared by the invention to indoor air treatment, the air quantity is 15 m3The self-made small purifier for purifying formaldehyde is filled with about 50 g of activated carbon and placed at 1M3In the experiment cabin; dropwise adding formaldehyde into the experimental cabin to ensure that the formaldehyde in the cabin is balanced at 1.0 +/-0.2 mg/m for carrying out heavy planting (the initial concentration is 10 +/-2 times of the concentration limit specified in GB/T18883); and (3) starting a power switch of the purifier, starting the purifier to work, sampling and testing the concentration of the formaldehyde in the cabin after timing for 1 hour, and calculating the formaldehyde purification efficiency.
Note: the concentration of formaldehyde was measured using a chemical absorption method.
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) the method has no high-temperature operation flow, and the activated carbon is naturally dried at room temperature after being impregnated and loaded with high-boiling-point acid and organic amine; 3) the preparation cost of the formaldehyde purification activated carbon is greatly reduced; 4) the active carbon rapid adsorption-acidic environment reinforced formaldehyde-liquid membrane mass transfer-formaldehyde and organic amine liquid-liquid reaction technology is coupled, and the formaldehyde purification active carbon with higher activity is prepared
In addition to the above embodiments, the present invention may have other embodiments, and any technical solutions formed by equivalent substitutions or equivalent transformations are within the scope of the present invention as claimed.
Claims (10)
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 impregnation liquid containing high-boiling-point acid and organic amine;
s2: soaking the soaking solution obtained in the step S1 and activated carbon in equal volume to obtain soaked activated carbon;
s3: and (4) flatly laying the impregnated activated carbon obtained in the step S2, ventilating and air-drying to obtain the formaldehyde purification activated carbon.
2. The method for preparing the formaldehyde purification activated carbon with low cost and high activity as claimed in claim 1, wherein the method comprises the following steps: in the step S1, the high-boiling acid includes one or two of sulfuric acid and phosphoric acid.
3. The method for preparing the formaldehyde purification activated carbon with low cost and high activity as claimed in claim 1, wherein the method comprises the following steps: in the step S1, the organic amine includes one or more of ethylene urea, diethylamine, diethylenetriamine, triethylenetetramine and amino acids; wherein, the amino acid substances comprise: glycine, aspartic acid, glutamic acid, cysteine, lysine, histidine and arginine.
4. The method for preparing the formaldehyde purification activated carbon with low cost and high activity as claimed in claim 1, wherein the method comprises the following steps: 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 active carbon is 0.1-1.0:15, and the soaking time is 6-24 hours; in the step S2, the equal volume of the impregnation solution is calculated according to the saturated water absorption of the required activated carbon.
5. The method for preparing the formaldehyde purification activated carbon with low cost and high activity as claimed in claim 1, wherein the method comprises the following steps: in the step S3, the activated carbon is spread flatly, ventilated and air-dried, in order to uniformly spread the impregnated activated carbon at room temperature, natural ventilation is carried out to volatilize part of moisture absorbed by the activated carbon, the air-drying time is determined according to the temperature at room temperature, and sampling and weighing are carried out until the moisture content in the material is 20-40%, thus obtaining the formaldehyde purification activated carbon.
6. The method for preparing the formaldehyde purification activated carbon with low cost and high activity as claimed in claim 1, wherein the method comprises the following steps: weighing 100 g of coal columnar activated carbon, wherein the saturated water absorption of the coal columnar activated carbon is 76% of the mass of the coal columnar activated carbon; weighing 76 ml of deionized water in a beaker, weighing 5 g of sulfuric acid and 5 g of ethylene urea, and dissolving to prepare a dipping solution; mixing the impregnation liquid with the activated carbon, uniformly stirring, and standing for 12 h; the activated carbon was spread on a screen and air dried naturally at an indoor temperature of 28 ℃ for 6 hours, and the mass of the activated carbon was 159 g, at which time the water content of the material was 31%.
7. The method for preparing the formaldehyde purification activated carbon with low cost and high activity as claimed in claim 1, wherein the method comprises the following steps: weighing 100 g of coal columnar activated carbon, wherein the saturated water absorption of the coal columnar activated carbon is 76% of the mass of the coal columnar activated carbon; weighing 76 ml of deionized water in a beaker, weighing 3 g of phosphoric acid and 6 g of glycine, and dissolving to prepare a steeping fluid; mixing the impregnation liquid with the active carbon, uniformly stirring, and standing for 10 h; the activated carbon is laid on a screen mesh and naturally dried at the indoor temperature of 30 ℃ for 6 hours, and the weight of the activated carbon is 145 g, and the water content of the material is 25%.
8. The method for preparing the formaldehyde purification activated carbon with low cost and high activity as claimed in claim 1, wherein the method comprises the following steps: weighing 100 g 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 70 ml of deionized water in a beaker, weighing 3 g of phosphoric acid, 3 g of sulfuric acid and 8 g of diethylamine, and dissolving to prepare a dipping solution; mixing the impregnation liquid with the active carbon, uniformly stirring, and standing for 8 hours; the activated carbon was spread on a screen and air dried naturally at an indoor temperature of 28 ℃ for 6 hours, and the mass of the activated carbon was 158 g, at which time the water content of the material was 28%.
9. The method for preparing the formaldehyde purification activated carbon with low cost and high activity as claimed in claim 1, wherein the method comprises the following steps: weighing 100 g 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 70 ml of deionized water in a beaker, and weighing 8 g of sulfuric acid and 10 g of glutamic acid to dissolve to prepare a steeping fluid; mixing the impregnation liquid with the activated carbon, uniformly stirring, and standing for 24 hours; the activated carbon was spread on a screen and air dried naturally at 25 ℃ in room temperature for 6 hours, and the mass of the activated carbon was 176 g, at which time the water content of the material was 33%.
10. The method for preparing the formaldehyde purification activated carbon with low cost and high activity as claimed in claim 1, wherein the method comprises the following steps: weighing 100 g 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 70 ml of deionized water in a beaker, weighing 7 g of sulfuric acid, 5 g of ethylene urea and 4 g of glycine, and dissolving to prepare a dipping solution; mixing the impregnation liquid with the activated carbon, uniformly stirring, and standing for 18 h; the activated carbon is laid on a screen mesh and naturally dried at the indoor temperature of 26 ℃ for 10 hours, and the weight of the activated carbon is 145 g, and the water content of the material is 20%.
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