CN114797438A - Formaldehyde scavenging agent, preparation method and application thereof - Google Patents
Formaldehyde scavenging agent, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a formaldehyde scavenger, a preparation method and application thereof. The preparation method grows platinum on the nitrogen-doped cerium dioxide/activated diatomite composite material to obtain the formaldehyde scavenger. The formaldehyde scavenger prepared by the invention improves the adsorption effect of formaldehyde molecules on the surface of the scavenger, further promotes the catalytic degradation, effectively converts the formaldehyde molecules into carbon dioxide, and does not generate toxic and harmful substances. The formaldehyde scavenger prepared by the invention has excellent removal performance when being applied to formaldehyde in a closed room, and can be used for a long time.
Description
Technical Field
The invention belongs to the field of environment-friendly materials, and particularly relates to a formaldehyde scavenger, a preparation method and application thereof.
Background
The development of industry obviously improves the living standard of people, but along with the wide application of chemical raw materials such as urea-formaldehyde resin and the like, the industry also brings certain harm to people, and the formaldehyde in the environment is excessive. Formaldehyde is a prototoxin that binds to proteins causing allergic reactions in the local skin and even the whole body. The harm caused by formaldehyde to people varies from person to person. The most sensitive to formaldehyde is the human eye, followed by the respiratory system, where the respiratory tract is most vulnerable to formaldehyde. On the other hand, formaldehyde is a hapten, which binds to proteins in the human body to form an antigen, causing skin diseases such as allergic dermatitis. When a human body is contacted with formaldehyde for a long time, anaphylactic reaction and abnormal smell can occur, the immunologic function and the cardio-pulmonary respiratory function of the human body are seriously influenced, and various complications such as inappetence, night sweating, abdominal swelling and pain, irregular pulse, dermatitis, weakness, irregular change of body temperature, eczema, redness and swelling, headache and the like occur. In severe cases, it can cause irritation and ulceration of the skin tissue and even carcinogenesis. According to the modern medical journal, formaldehyde also causes gene mutation in cell nucleus and causes leukemia and chromosome abnormality. Has the greatest harm to the old, the weak, the pregnant women and the children.
The house is the most important workplace and living place for people, and most of the time is spent here. After house decoration, formaldehyde exceeds the standard and certain pungent smell is generated. Formaldehyde is highly toxic and is identified by the world health organization as a carcinogenic and teratogenic substance. Excessive formaldehyde seriously harms the health of people and can cause a series of problems of respiratory diseases, newborn physique reduction, chromosome abnormality, even leukemia and the like.
People usually choose to ventilate a newly-decorated house for a period of time and use a formaldehyde scavenger for treatment, so as to achieve the aim of removing formaldehyde; the formaldehyde release period of the decoration material is as long as 3 to 15 years, so that the formaldehyde in the room can be quickly and effectively removed, and the formaldehyde-free decoration material is very necessary for physical and psychological health of people.
CN 103143231A discloses a mineral crystal formaldehyde scavenger for decoration, which consists of 10-15 parts of attapulgite, 10-15 parts of bentonite, 10-15 parts of sepiolite, 2-4 parts of diatomite, 10-15 parts of zeolite, 10-15 parts of zirconium phosphate and 10-15 parts of nano titanium dioxide; the invention has strong air purificationHas good effect in eliminating formaldehyde. CN 104874267A discloses a formaldehyde scavenger, which is prepared from 4-8 parts of bentonite, 0.5-1.5 parts of tea polyphenol, 1-3 parts of amino acid, 80-90 parts of a sodium sulfate-hydrogen peroxide-sodium chloride adduct, 1-5 parts of anatase titanium dioxide and 1-5 parts of sodium dodecyl benzene sulfonate; the invention is healthy and environment-friendly, and can effectively remove formaldehyde. CN 104492023A discloses a formaldehyde scavenger, which is prepared from 65-70% of lysimachia foenum-graecum powder, 25-25% of ammonium bicarbonate and CaCl 2 5-10 percent of the formaldehyde scavenger can effectively remove formaldehyde in rooms, automobiles and furniture.
The methods are simple to operate, have good effect on removing formaldehyde in a short time, but the formaldehyde in the decoration materials is slowly released. The formaldehyde can be quickly removed by using the existing formaldehyde scavenger, the indoor formaldehyde content can slowly rise after a period of time, and the formaldehyde scavenger needs to be replaced by a new formaldehyde scavenger, so that the performance of removing the formaldehyde for a long time by using the formaldehyde scavenger is also remarkable. The prior art lacks an evaluation of formaldehyde degradation products and many catalysts, while capable of reducing indoor formaldehyde levels, may produce irritating formic acid and toxic and harmful carbon monoxide. Therefore, it is necessary to develop a formaldehyde scavenger which has high efficiency and long formaldehyde removal capacity, and simultaneously evaluate the formaldehyde generation catalysis product.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a formaldehyde scavenger capable of removing formaldehyde rapidly and effectively and maintaining stable removal performance for a long time, and evaluates the product of catalyzing formaldehyde.
In order to achieve the aim, the invention provides a preparation method of a formaldehyde scavenger, which comprises the following steps:
step 1: dispersing activated diatomite, a nitrogen source and a cerium source in water under stirring to form uniform suspension I;
step 2: dropwise adding the reaction solution into the suspension I which is continuously stirred, stirring for reaction, performing suction filtration to obtain a filter cake, washing and drying; calcining the dried filter cake, naturally cooling, crushing and sieving to obtain cerium dioxide/activated diatomite composite material powder;
and step 3: uniformly dispersing the cerium dioxide/activated diatomite composite material powder obtained in the step 2 in water under ultrasound to form a suspension II; adding chloroplatinic acid into the continuously stirred suspension, and continuously stirring; adding a reducing agent solution for reaction, carrying out suction filtration, washing and drying to obtain the formaldehyde scavenger.
Preferably, the weight ratio of the activated diatomite, the nitrogen source, the cerium source and the water in the step 1 is 100: (1-5): (10-20): 1000, parts by weight; the nitrogen source is one of urea, dicyandiamide and glycine; the cerium source is cerium nitrate hexahydrate; the stirring speed is 300-500 r/min, and the stirring time is 1-3 h; the preparation method of the activated diatomite comprises the following steps: soaking 10-20 parts of 500-1000-mesh diatomite in 100-300 parts of 0.5-3 mol/L hydrochloric acid or nitric acid aqueous solution for 1-3 hours; washing with water until the pH value of the supernatant is 6.5-7.5, performing suction filtration, putting the filter cake into a constant-temperature oven, drying at 60-100 ℃ for 3-5 h, crushing the filter cake, sieving with a 500-1000-mesh sieve, and collecting the powder passing through the sieve to obtain the activated diatomite.
Preferably, the reaction solution in the step 2 is one of sodium hydroxide, ammonia water, sodium carbonate and sodium bicarbonate aqueous solution, the concentration is 0.6-2 mol/L, and the weight ratio of the reaction solution to water in the suspension is 1: (10-20); the dropwise adding is carried out at a speed of 10-30 g/min in a constant-pressure funnel; the stirring speed of the suspension I is 300-500 r/min; the washing is carried out by using ethanol and water for three times respectively; the drying is to dry the filter cake in a constant-temperature oven at 60-100 ℃ for 3-5 h; the calcining temperature is 500-700 ℃, and the calcining time is 3-5 h; and sieving the powder by using a sieve of 500-1000 meshes, and collecting the powder passing through the sieve.
Preferably, the ultrasonic power in the step 3 is 50-200W, the frequency is 20-130 KHz, the temperature is 20-40 ℃, and the time is 20-60 min; the stirring speed is 300-500 r/min; the weight ratio of the cerium dioxide/diatomite composite material, water, chloroplatinic acid and the reducing agent solution is 10: 100: (0.1-0.5): (1-5), wherein the reducing agent solution is an ascorbic acid aqueous solution, and the concentration is 0.5-1 mol/L; adding a reducing agent solution, and then continuing to react for 1-2 h at a stirring speed of 300-500 r/min; the washing is carried out by using ethanol and water for three times respectively; the drying is to place the mixture into a constant-temperature oven to be dried for 3-5 hours at the temperature of 60-100 ℃.
Preferably, the dried filter cake in the step 3 can be crushed into powder or processed and molded by a granulator and then put into a breathable non-woven cloth bag to be matched with different scenes for use; the crushing step is that the dried filter cake is crushed, the crushed filter cake passes through a screen of 500-1000 meshes, and the powder passing through the screen is collected to obtain formaldehyde scavenger powder; the granulation processing is to put the dry filter cake into a granulator to prepare a spherical shape with the diameter of 8-20 mm or a columnar shape with the diameter of 6mm and the height of 10 mm.
Another aspect of the present invention provides the use of the above formaldehyde scavenger:
and (3) measuring the concentration of formaldehyde after the newly-decorated house is closed, placing the formaldehyde scavenger, and testing the concentration of the formaldehyde in the closed environment after a period of time. The house area is 20-30 m 2 (ii) a Uniformly placing the breathable non-woven fabric bag filled with the formaldehyde scavenger in a closed house, wherein the application density is 2-5 g/m 2 。
The formaldehyde concentration test method is based on the second part of the public place sanitation test method GB/T18204.2-2014, namely chemical pollutants, and formaldehyde is tested by using a phenol reagent spectrophotometry or is detected by using an infrared photoacoustic gas monitor.
The invention has the beneficial effects that:
1. the invention provides a preparation method of a novel formaldehyde scavenger, which is characterized in that cerium dioxide, nitrogen doping and metal platinum are introduced into activated diatomite, so that the degradation and removal capacity of a composite material to formaldehyde is remarkably improved, the nitrogen doping enhances the dispersibility of the metal platinum, the oxygen vacancy of the cerium dioxide, active oxygen species gathered on the surface of the metal platinum and the larger specific surface area of the diatomite generate a synergistic effect, and the composite material has extremely high degradation capacity to formaldehyde at room temperature.
2. The preparation method is simple, can effectively remove formaldehyde, has effective action time of more than half a year, can be processed into different shapes according to requirements, is matched with different use scenes, and is very convenient to use.
Drawings
FIG. 1 variation of formaldehyde conversion at different relative humidities for formaldehyde scavengers prepared in example 3.
Detailed Description
Part of the raw materials used in the invention are introduced as follows:
diatomite is a kind of biological deposited siliceous rock and is formed by remains of diatom after long-term natural environment action, and the main component is SiO 2 The amorphous protein mineral of (1); the diatomite is non-toxic and odorless, exists in a large amount in a natural environment, has high purity, and is low in obtaining cost, and the price of the diatomite is about one twentieth of that of the activated carbon; diatomaceous earth can be divided into, according to the difference of its algal shells: the diatom ooze comprises straight-chain algae, Cyclotella, round sieve algae, granular straight-chain algae, Cladosiphon okamuranus, and the like, and the diatomite also contains oxides of metal ions such as alumina, ferric oxide, and the like; the diatomite is widely used as a reaction catalyst, a filling agent, a heat insulation material, a filtering material and the like because the wall shell is composed of a plurality of multistage, large-quantity and orderly-arranged micropores, has the characteristics of light weight, more holes, large specific surface area, strong adsorption capacity and stable chemical properties (except hydrofluoric acid and strong alkali under high temperature and high pressure which are basically insoluble), the surface of the diatomite is covered by a plurality of silicon hydroxyl groups, the relation with the adsorption properties is close, besides the silicon hydroxyl groups, the surface of the diatomite also contains a plurality of hydroxyl groups, the diatomite used in the invention is collected in a region near the river in Jilin province, and the main components of the diatomite are silicon dioxide, aluminum oxide, ferric oxide, calcium oxide and magnesium oxide;
cerium nitrate hexahydrate of the formula Ce (NO) 3 ) 3 ·6H 2 O, inorganic oxidant, when meeting the fire of combustible material, can help the fire behavior; mixing with reducing agent, organic matter, and inflammable matter such as sulfur, phosphorus or metal powder to form explosive mixture, which decomposes at high temperature to release toxic nitrogen oxide gas; the industrial product is reddish, deliquescent, harmful to environment, has accumulation in underground water, can be used as gas lamp gauze cover additive and petrochemical catalyst, is used as raw material for preparing cerium salt, can be used as analytical reagent in analytical chemistry and also can be used in pharmaceutical industryThe cerous nitrate hexahydrate used in the invention is purchased from national chemical reagent company Limited;
glycine, also known as glycine, is a non-essential amino acid of formula C 2 H 5 NO 2 The solid glycine is white to off-white crystalline powder, is odorless and nontoxic, is easily soluble in water, and is almost insoluble in ethanol or diethyl ether; the glycine is used for pharmaceutical industry, biochemical test and organic synthesis, is an amino acid with the simplest structure, has acidic and basic functional groups in molecules, can be ionized in water, has strong hydrophilicity, belongs to nonpolar amino acid, is soluble in polar solvent but insoluble in nonpolar solvent, has higher boiling point and melting point, can be made to present different molecular forms by adjusting the acidity and basicity of aqueous solution, and is purchased from national chemical reagent company Limited;
chloroplatinic acid of the formula H 2 PtCl 6 ·6H 2 O, also known as hexachloroplatinic (IV) acid, contains six crystal waters, is orange yellow powder or russet crystal, is easily deliquescent, is soluble in water, ethanol and acetone, and is an active ingredient of a hydrogenation dehydrogenation catalyst in petrochemical industry; the method is commonly used as a chemical reagent and a catalyst, the precipitation of alkaloid, the preparation of a noble metal catalyst and the coating of noble metal, and the chloroplatinic acid used in the method is purchased from chemical reagent Limited of the national medicine group;
ascorbic acid, also known as vitamin C, is a polyhydroxy compound having the formula C 6 H 8 O 6 The structure is similar to glucose, and two adjacent enol-type hydroxyl groups at the 2 nd and 3 rd positions in the molecule are easy to dissociate so as to release H + Therefore, the ascorbic acid has the property of acid, also called L-ascorbic acid, has a lactone ring, has 2 chiral carbon atoms, is active in property, has optical activity and strong reducibility, is easily oxidized into dehydroascorbic acid, is white crystal or crystalline powder, is odorless, is sour in taste, changes slightly yellow in color after being placed for a long time, is easy to dissolve in water, is acidic, is slightly soluble in ethanol and is insoluble in trichloromethane or diethyl ether, and the ascorbic acid used in the method is purchased from national chemical reagent Limited company;
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
EXAMPLE 1 preparation of a Formaldehyde scavenger
Dispersing 100g of activated diatomite, 5g of urea and 20g of cerous nitrate hexahydrate in 1000g of water, and stirring at a stirring speed of 500r/min for 1h to form a uniform suspension I; placing 100g of 0.6mol/L ammonia water solution in a constant-pressure funnel, dripping the ammonia water solution into the suspension I stirred at the stirring speed of 500r/min at the speed of 20g/min, continuously stirring for reacting for 2 hours, carrying out suction filtration, washing with ethanol and water for three times respectively, transferring the filter cake to a constant-temperature oven, and drying at 80 ℃ for 3 hours to obtain a dried filter cake; calcining the dried filter cake in a muffle furnace at 600 ℃ for 2h, naturally cooling, crushing the calcined filter cake, sieving with a 500-mesh sieve, and collecting powder below the sieve to obtain cerium dioxide/diatomite composite material powder;
dispersing 10g of cerium dioxide/activated diatomite composite material powder into 100g of water at the ultrasonic power of 100W, the frequency of 50KHz and the temperature of 25 ℃ to form a uniform suspension II; continuously stirring the suspension II at a stirring speed of 500r/min, adding 0.5g of chloroplatinic acid into the continuously stirred suspension II, continuously stirring and dispersing for 1h, adding 5g of 0.5mol/L ascorbic acid aqueous solution, and continuously stirring and reacting for 2h at 500 r/min; performing suction filtration, washing with ethanol and water for three times respectively, transferring the filter cake to a constant-temperature oven, drying at 80 ℃ for 3 hours to obtain a dried filter cake, crushing the dried filter cake, sieving with a 500-mesh sieve, and collecting powder below the sieve, namely the formaldehyde scavenger prepared in the embodiment;
the preparation method of the activated diatomite comprises the following steps: 100g of 500-mesh diatomite is placed in 1000g of 2mol/L hydrochloric acid to be soaked for 3 hours; washing with water until the pH of the supernatant is 7.0, performing suction filtration, drying the filter cake in a constant-temperature oven at 100 ℃ for 4h, crushing the filter cake, sieving with a 500-mesh sieve, and collecting the powder passing through the sieve to obtain the activated diatomite.
EXAMPLE 2 preparation of a Formaldehyde scavenger
Dispersing 100g of activated diatomite, 5g of dicyandiamide and 20g of cerium nitrate hexahydrate in 1000g of water, and stirring at a stirring speed of 500r/min for 1h to form uniform suspension I; placing 100g of 0.6mol/L ammonia water solution in a constant-pressure funnel, dripping the ammonia water solution into the suspension I stirred at the stirring speed of 500r/min at the speed of 20g/min, continuously stirring for reaction for 2 hours, carrying out suction filtration, washing with ethanol and water for three times respectively, transferring the filter cake to a constant-temperature oven, and drying at 80 ℃ for 3 hours to obtain a dried filter cake; calcining the dried filter cake in a muffle furnace at 600 ℃ for 2h, naturally cooling, crushing the calcined filter cake, sieving with a 500-mesh sieve, and collecting powder below the sieve to obtain cerium dioxide/activated diatomite composite material powder;
dispersing 10g of cerium dioxide/activated diatomite composite material powder into 100g of water under the ultrasonic power of 100W, the frequency of 50KHz and the temperature of 25 ℃ to form a uniform suspension II; continuously stirring the suspension II at a stirring speed of 500r/min, adding 0.5g of chloroplatinic acid into the continuously stirred suspension II, continuously stirring and dispersing for 1h, adding 5g of 0.5mol/L ascorbic acid aqueous solution, and continuously stirring and reacting for 2h at 500 r/min; performing suction filtration, washing with ethanol and water for three times respectively, transferring the filter cake to a constant-temperature oven, drying at 80 ℃ for 3 hours to obtain a dried filter cake, crushing the dried filter cake, sieving with a 500-mesh sieve, and collecting powder below the sieve, namely the formaldehyde scavenger prepared in the embodiment;
the activated diatomaceous earth was prepared in the same manner as in example 1.
EXAMPLE 3 preparation of a Formaldehyde scavenger
Dispersing 100g of activated diatomite, 5g of glycine and 20g of cerous nitrate hexahydrate in 1000g of water, and stirring at a stirring speed of 500r/min for 1h to form a uniform suspension I; placing 100g of 0.6mol/L ammonia water solution in a constant-pressure funnel, dripping the ammonia water solution into the suspension I stirred at the stirring speed of 500r/min at the speed of 20g/min, continuously stirring for reaction for 2 hours, carrying out suction filtration, washing with ethanol and water for three times respectively, transferring the filter cake to a constant-temperature oven, and drying at 80 ℃ for 3 hours to obtain a dried filter cake; calcining the dried filter cake in a muffle furnace at 600 ℃ for 2h, naturally cooling, crushing the calcined filter cake, sieving with a 500-mesh sieve, and collecting powder below the sieve to obtain cerium dioxide/activated diatomite composite material powder;
dispersing 10g of cerium dioxide/activated diatomite composite material powder into 100g of water under the ultrasonic power of 100W, the frequency of 50KHz and the temperature of 25 ℃ to form a uniform suspension II; continuously stirring the suspension II at a stirring speed of 500r/min, adding 0.5g of chloroplatinic acid into the continuously stirred suspension II, continuously stirring and dispersing for 1h, adding 5g of 0.5mol/L ascorbic acid aqueous solution, and continuously stirring and reacting for 2h at 500 r/min; performing suction filtration, washing with ethanol and water for three times respectively, transferring the filter cake to a constant-temperature oven, drying at 80 ℃ for 3 hours to obtain a dried filter cake, crushing the dried filter cake, sieving with a 500-mesh sieve, and collecting powder below the sieve, namely the formaldehyde scavenger prepared in the embodiment;
the activated diatomaceous earth was prepared in the same manner as in example 1.
Comparative example 1 preparation of a Formaldehyde scavenger
Dispersing 100g of activated diatomite and 20g of cerous nitrate hexahydrate in 1000g of water, and stirring at a stirring speed of 500r/min for 1h to form uniform suspension I; placing 100g of 0.6mol/L ammonia water solution in a constant-pressure funnel, dripping the ammonia water solution into the suspension I stirred at the stirring speed of 500r/min at the speed of 20g/min, continuously stirring for reacting for 2 hours, carrying out suction filtration, washing with ethanol and water for three times respectively, transferring the filter cake to a constant-temperature oven, and drying at 80 ℃ for 3 hours to obtain a dried filter cake; calcining the dried filter cake in a muffle furnace at 600 ℃ for 2h, naturally cooling, crushing the calcined filter cake, sieving with a 500-mesh sieve, and collecting powder below the sieve to obtain cerium dioxide/activated diatomite composite material powder;
dispersing 10g of cerium dioxide/activated diatomite composite material powder in 100g of water under the conditions of ultrasonic power of 100W, frequency of 50KHz and temperature of 25 ℃ and performing ultrasonic treatment for 1 hour to form a uniform suspension II; continuously stirring the suspension II at a stirring speed of 500r/min, adding 0.5g of chloroplatinic acid into the continuously stirred suspension II, continuously stirring and dispersing for 1h, adding 5g of 0.5mol/L ascorbic acid aqueous solution, and continuously stirring and reacting for 2h at 500 r/min; performing suction filtration, washing with ethanol and water for three times respectively, transferring the filter cake to a constant-temperature oven, drying at 80 ℃ for 3 hours to obtain a dried filter cake, crushing the dried filter cake, sieving with a 500-mesh sieve, and collecting powder below the sieve, namely the formaldehyde scavenger prepared in the embodiment;
the activated diatomaceous earth was prepared in the same manner as in example 1.
Comparative example 2 preparation of a Formaldehyde scavenger
Dispersing 100g of 500-mesh diatomite, 5g of glycine and 20g of cerous nitrate hexahydrate in 1000g of water, and stirring at a stirring speed of 500r/min for 1 hour to form a uniform suspension I; placing 100g of 0.6mol/L ammonia water solution in a constant-pressure funnel, dripping the ammonia water solution into the suspension I stirred at the stirring speed of 500r/min at the speed of 20g/min, continuously stirring for reaction for 2 hours, carrying out suction filtration, washing with ethanol and water for three times respectively, transferring the filter cake to a constant-temperature oven, and drying at 80 ℃ for 3 hours to obtain a dried filter cake; calcining the dried filter cake in a muffle furnace at 600 ℃ for 2h, naturally cooling, crushing the calcined filter cake, sieving with a 500-mesh sieve, and collecting powder below the sieve to obtain cerium dioxide/diatomite composite material powder;
dispersing 10g of cerium dioxide/diatomite composite material powder in 100g of water under the conditions of ultrasonic power of 100W, frequency of 50KHz and temperature of 25 ℃ and performing ultrasonic treatment for 1 hour to form a uniform suspension II; continuously stirring the suspension II at a stirring speed of 500r/min, adding 0.5g of chloroplatinic acid into the continuously stirred suspension II, continuously stirring and dispersing for 1h, adding 5g of 0.5mol/L ascorbic acid aqueous solution, and continuously stirring and reacting for 2h at 500 r/min; and (3) performing suction filtration, washing with ethanol and water for three times respectively, transferring the filter cake to a constant-temperature oven, drying at 80 ℃ for 3 hours to obtain a dried filter cake, crushing the dried filter cake, sieving with a 500-mesh sieve, and collecting powder below the sieve, namely the formaldehyde scavenger prepared in the embodiment.
Comparative example 3 preparation of a Formaldehyde scavenger
Dispersing 100g of activated diatomite, 5g of glycine and 20g of cerous nitrate hexahydrate in 1000g of water, and stirring at a stirring speed of 500r/min for 1 hour to form a uniform suspension I; placing 100g of 0.6mol/L ammonia water solution in a constant-pressure funnel, dripping the ammonia water solution into the suspension I stirred at the stirring speed of 500r/min at the speed of 20g/min, continuously stirring for reaction for 2 hours, carrying out suction filtration, washing with ethanol and water for three times respectively, transferring the filter cake to a constant-temperature oven, and drying at 80 ℃ for 3 hours to obtain a dried filter cake; placing the dried filter cake in a muffle furnace at 600 ℃ for calcining for 2h, naturally cooling, crushing the calcined filter cake, sieving with a 500-mesh sieve, and collecting powder below the sieve, namely the formaldehyde scavenger prepared in the comparative example;
the activated diatomaceous earth was prepared in the same manner as in example 1.
Comparative example 4 preparation of a Formaldehyde scavenger
Dispersing 100g of activated diatomite and 5g of glycine in 1000g of water under the conditions of ultrasonic power of 100W, frequency of 50KHz and temperature of 25 ℃ and performing ultrasonic treatment for 1 hour to form uniform suspension I; the suspension I is subjected to filtration; continuously stirring at the stirring speed of 500r/min, adding 0.5g of chloroplatinic acid into the continuously stirred suspension II, continuously stirring and dispersing for 1h, adding 5g of 0.5mol/L ascorbic acid aqueous solution, and continuously stirring at 500r/min for reaction for 2 h; and (3) performing suction filtration, washing with ethanol and water for three times respectively, transferring the filter cake to a constant-temperature oven, drying at 80 ℃ for 3 hours to obtain a dried filter cake, crushing the dried filter cake, sieving with a 500-mesh sieve, and collecting powder below the sieve, namely the formaldehyde scavenger prepared in the embodiment.
Test example 1 analysis of catalytic Properties of Formaldehyde scavenger
The formaldehyde degradation test is carried out in a self-made reaction box, the size of the reaction box is 20cm multiplied by 40cm, the material of the reaction box is light-tight and can not adsorb formaldehyde and other gases, the temperature in the reaction box is 25 ℃ at room temperature, and the relative humidity is 50%. The formaldehyde concentration was monitored with an infrared photoacoustic gas detector. Respectively covering 100mg of the formaldehyde scavengers prepared in the embodiment 3 and the comparative examples 1-4 by using culture dishes, putting the culture dishes into a reaction box, injecting 20 mu L of formaldehyde aqueous solution with the mass fraction of 38% into the reaction box, and sealing the reaction box; when the formaldehyde concentration was 300ppm, the dish was opened to allow the formaldehyde scavenger to contact the formaldehyde and initiate the catalytic reaction. The changes in the concentrations of formaldehyde and carbon dioxide in the test chamber were monitored over 1 hour to complete the performance evaluation of the formaldehyde scavengers prepared in example 3 and comparative examples 1-4 of the present invention.
The results of the conversion of formaldehyde into carbon dioxide by the remover are shown in table 1, and it can be seen that the conversion rate of the comparative example 3 containing no platinum to formaldehyde is 0, because the formaldehyde molecules are only adsorbed on the surface of the remover and are not degraded, the concentration of formaldehyde in the system is reduced, and no carbon dioxide is generated; however, the degradation of formaldehyde by other formaldehyde scavengers is shown by a decrease in formaldehyde concentration and an increase in carbon dioxide concentration, and these results indicate that formaldehyde is degraded and converted into carbon dioxide; platinum has great promotion effect on formaldehyde degradation at room temperature of 25 ℃. The formaldehyde scavenger prepared in comparative example 4 has a weak degradation activity to formaldehyde, which indicates that ceria has a significant effect of improving catalytic degradation, and it is likely that ceria provides oxygen vacancies to greatly promote the formaldehyde catalytic reaction. As shown in table 1, example 3 exhibited higher catalytic performance with 96.2% conversion to formaldehyde over 1h relative to comparative example 1 prepared without glycine and comparative example 2 prepared without activated diatomaceous earth. The significant improvement in catalytic performance may be due to the fact that the surface of the activated diatomite in the formaldehyde scavenger prepared in example 3 is prone to generate a large amount of hydroxyl groups, which is helpful for the adsorption of formaldehyde molecules on the surface of the scavenger; glycine added in the preparation process has a uniform dispersion effect on cerium ions, so that the agglomeration of cerium dioxide is reduced, the doping of nitrogen after calcination is beneficial to the dispersion of platinum, and more active sites are improved; the presence of oxygen vacancies within the ceria greatly facilitates the degradation reaction. The effects generate good synergistic effect, improve the adsorption effect of formaldehyde molecules on the surface of the scavenging agent, further promote the catalytic degradation, and effectively convert the formaldehyde molecules into carbon dioxide.
TABLE 1 conversion of Formaldehyde scavenger
The formaldehyde scavenger prepared in example 3 of the present invention was subjected to a cyclic degradation test at room temperature of 25 c, a relative humidity of 50%, and an initial formaldehyde concentration of 300 ppm. The results show that the catalytic activity is not obviously reduced compared with the first test after continuous 5 times of circulation, which shows that the catalyst has stable performance and the capability of effectively degrading formaldehyde for a long time.
The formaldehyde scavenger prepared in inventive example 3 was subjected to a formaldehyde degradation test at a relative humidity of 5% to 85%, a room temperature of 25 ℃, and an initial formaldehyde concentration of 300ppm, and the results are shown in fig. 1, in which the conversion rate is a standard for the generation of carbon dioxide. The result shows that when the relative humidity is 15-65%, the conversion rate of the scavenging agent to formaldehyde is above 85%; conversion was 68.2% at a relative humidity of 5%; the conversion was 72.6% at a relative humidity of 85%. These results show that it is well resistant to common indoor conditions and does not produce toxic and harmful gases in everyday use. The relatively high humidity contributes to the degradation of formaldehyde, probably because the water vapor contributes to the formation of hydroxyl groups on the surface due to the high humidity, and the adsorption of formaldehyde is enhanced, so that the degradation capability of formaldehyde is enhanced; the proper amount of water vapor can inhibit the dynamic loss of surface hydroxyl in the formaldehyde oxidation reaction process, and is beneficial to the degradation reaction of formaldehyde; however, in the case of too high relative humidity, excessive water molecules may form competitive adsorption with formaldehyde, occupy a part of adsorption sites, and even block mass transfer channels, thereby reducing catalytic activity.
Test example 2 analysis of Formaldehyde scavenger catalyst product
The intermediates and oxidation processes of the degradation products that degrade formaldehyde were analyzed using an in situ infrared spectrometer. 100mg of the formaldehyde scavenger prepared in the example 3 is put into a reaction tank, mixed airflow of formaldehyde and nitrogen is introduced, and the reaction tank is kept for 1 hour; the oxygen flow was then maintained for 1 h. The formaldehyde concentration in the initial mixed gas stream was 50 ppm.
When the mixed gas flow is formaldehyde and nitrogen, the infrared peaks of the absorbed formaldehyde molecules and formate species are gradually enhanced along with the increase of time; the stretching vibration peak of O-C-O of dioxymethylene appears; and the infrared peak of the hydroxyl group gradually decreases. This indicates that the formaldehyde molecule is converted to a formate species and dioxymethylene, while the hydroxyl is consumed in the process. However, when oxygen is introduced, the infrared peaks of formaldehyde molecules and formate species are remarkably reduced, and the stretching vibration peak of O-C-O of dioxymethylene gradually disappears, and the results show that the formate species is further converted, and formaldehyde molecules adsorbed on the surface are rapidly degraded.
The formaldehyde is divided into two stages of adsorption and degradation on the surface of the scavenging agent. Formaldehyde molecules are firstly combined on the surface of the scavenging agent through hydrogen bonds; subsequently, the active oxygen atoms adjacent to the ceria surface attack the formaldehyde molecules to convert them to dioxymethylene intermediates, and thus to formate species; the formate species is further oxidized by the reactive oxygen species to carbonic acid, which is subsequently decomposed to carbon dioxide and water, which desorbs from the active sites on the scavenger surface, thereby regenerating the active sites. Hydroxyl groups adjacent to oxygen vacancies of cerium dioxide in the whole adsorption and degradation process can be regenerated through the reaction of surface adsorption water and active oxygen species, and finally the recovery of the formaldehyde removal capacity of the scavenging agent is realized.
These results show that the formaldehyde scavenger of example 3 of the present invention is effective in oxidizing formaldehyde to carbon dioxide without producing toxic and harmful intermediates.
Application example 1 application of Formaldehyde scavenger to removal of free Formaldehyde in closed House
The formaldehyde scavenger filter cake prepared by the method of example 3 was made into a column shape with a diameter of 6mm and a height of 10mm by a granulator, and 10g of the filter cake was divided and placed on a breathable nonwoven fabric tape for future use; a newly-decorated house with an area of 25m 2 And the formaldehyde concentration of the closed house is tested to be 0.61mg/m 3 (ii) a Placing 6 air-permeable non-woven fabrics bags with formaldehyde scavenger at multiple positions in the room, and testing the formaldehyde concentration in the room to be 0.04mg/m after three days 3 (ii) a The formaldehyde concentration in the room is continuously monitored, and the result shows that the formaldehyde concentration in the room is 0.06mg/m under the same condition after being used for six months 3 Still in the national standard of 0.1mg/m 3 The following. These results show that the formaldehyde scavenger prepared by the invention has the potential of rapidly and effectively scavenging free formaldehyde indoors for a long time.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. The preparation method of the formaldehyde scavenger is characterized by comprising the following steps:
step 1: dispersing activated diatomite, a nitrogen source and a cerium source in water under stirring to form a uniform suspension I;
step 2: dropwise adding the reaction solution into the suspension I which is continuously stirred, stirring for reaction, performing suction filtration to obtain a filter cake, washing and drying; calcining the dried filter cake, naturally cooling, crushing and sieving to obtain cerium dioxide/activated diatomite composite material powder;
and 3, step 3: uniformly dispersing the cerium dioxide/activated diatomite composite material powder obtained in the step 2 in water under ultrasound to form a suspension II; adding chloroplatinic acid into the continuously stirred suspension, and continuously stirring; adding a reducing agent solution for reaction, carrying out suction filtration, washing and drying to obtain a dry filter cake, namely the formaldehyde scavenger;
the weight ratio of the activated diatomite, the nitrogen source, the cerium source and the water in the step 1 is 100: (1-5): (10-20): 1000, parts by weight; the stirring speed is 300-500 r/min, and the stirring time is 1-3 h;
the weight ratio of the reaction solution to water in the suspension in the step 2 is 1: (10-20); the dropwise adding is carried out at a speed of 10-30 g/min in a constant-pressure funnel; the stirring speed of the suspension I is 300-500 r/min; the washing is carried out by using ethanol and water for three times respectively; the drying is to dry the filter cake in a constant-temperature oven at 60-100 ℃ for 3-5 h;
the ultrasonic power in the step 3 is 50-200W, the frequency is 20-130 KHz, the temperature is 20-40 ℃, and the time is 20-60 min; the stirring speed is 300-500 r/min; the weight ratio of the cerium dioxide/diatomite composite material, water, chloroplatinic acid and the reducing agent solution is 10: 100: (0.1-0.5): (1-5); adding a reducing agent solution, and then continuously reacting for 1-2 h at a stirring speed of 300-500 r/min; the washing is carried out by using ethanol and water for three times respectively; the drying is to place the mixture into a constant-temperature oven to dry for 3-5 hours at the temperature of 60-100 ℃.
2. The method of claim 1, wherein the activated diatomaceous earth in step 1 is prepared by: soaking 10-20 parts of 500-1000-mesh diatomite in 100-300 parts of 0.5-3 mol/L hydrochloric acid or nitric acid aqueous solution for 1-3 hours; washing with water until the pH value of the supernatant is 6.5-7.5, performing suction filtration, putting the filter cake into a constant-temperature oven, drying at 60-100 ℃ for 3-5 h, crushing the filter cake, sieving with a 500-1000-mesh sieve, and collecting the powder passing through the sieve to obtain the activated diatomite.
3. The method according to claim 1, wherein the nitrogen source in step 1 is one of urea, dicyandiamide and glycine.
4. The method for preparing the formaldehyde scavenger according to claim 1, wherein the reaction solution in the step 2 is an aqueous solution of any one of sodium hydroxide, ammonia water, sodium carbonate and sodium bicarbonate, and the concentration is 0.6-2 mol/L.
5. The method for preparing the formaldehyde scavenger according to claim 1, wherein the calcination temperature in the step 2 is 500-700 ℃, and the calcination time is 3-5 h; and sieving the powder by using a sieve of 500-1000 meshes, and collecting the powder passing through the sieve.
6. The method of claim 1, wherein the reducing agent solution in step 3 is 0.5-1 mol/L ascorbic acid solution.
7. The method for preparing the formaldehyde scavenger according to claim 1, wherein the dried filter cake obtained in the step 3 is pulverized, and the pulverized powder is passed through a 500-1000 mesh screen, and the powder passed through the screen is collected to obtain the formaldehyde scavenger powder.
8. The method for preparing the formaldehyde scavenger according to claim 1, wherein the dried filter cake obtained in the step 3 is granulated into formaldehyde scavengers with different shapes by a granulator, and the shapes are spheres with the diameter of 8-20 mm or columns with the diameter of 6mm and the height of 10 mm.
9. A formaldehyde scavenger prepared by the method according to any one of claims 1 to 8.
10. The use of the formaldehyde scavenger in a clean room according to claim 9, wherein the air-permeable nonwoven fabric bags filled with the formaldehyde scavenger are uniformly placed in the closed room, and the room area is 20-30 m 2 The application amount of the formaldehyde scavenger is 2-5 g/m 2 。
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